EP2855553B1 - Radiation-curable compounds - Google Patents

Radiation-curable compounds Download PDF

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Publication number
EP2855553B1
EP2855553B1 EP13724819.1A EP13724819A EP2855553B1 EP 2855553 B1 EP2855553 B1 EP 2855553B1 EP 13724819 A EP13724819 A EP 13724819A EP 2855553 B1 EP2855553 B1 EP 2855553B1
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Prior art keywords
group
hydroxy
printing
compound
phenyl
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EP13724819.1A
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German (de)
French (fr)
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EP2855553A1 (en
Inventor
Jürgen Kaczun
Reinhold Schwalm
David Trumbo
Eugene Valentine Sitzmann
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Igm Malta Ltd
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/905—Hydrophilic or hydrophobic cellular product

Definitions

  • the invention relates to low-viscosity formulations of radiation-curable compounds, processes for their preparation, their use and inks containing them, printing inks and printing varnishes.
  • DE 19501025 discloses vinyloxycarbonyl groups attached to photoinitiator systems which are also incorporatable in a free-radical polymerization.
  • the compounds disclosed there are variable only within narrow limits due to the limited possibilities of the spacer structures.
  • such compounds are often not fully reacted in UV polymerization and, as a result, can migrate out of the coating.
  • WO 03/68785 discloses reactions of acylphosphine oxide type photoinitiators with diisocyanates. Further functionalization of the free isocyanate groups is not disclosed.
  • WO 03/68783 discloses reactions of optionally hydroxyalkylated acylphosphine oxide photoinitiators with di- and polyisocyanates. Further functionalization of the free isocyanate groups is not disclosed.
  • EP 632329 discloses benzophenone, acetophenone or hydroxyacetophenone type photoinitiators which are functionalized with diisocyanates.
  • the isocyanates thus obtained can then be further derivatized, for example by reacting the free isocyanate group with hydroxyalkyl (meth) acrylates, so that photoinitiators are obtained which can be incorporated in a free-radical polymerization.
  • a disadvantage of this functionalization is that one can only achieve a low degree of functionalization by the use of diisocyanates.
  • DE 102 46 512 describes a different process for preparing the same compounds as in WO 00/39183 described, as well as different secondary products of these compounds. Also disclosed is the chemical coupling of polymerization stabilizers via free isocyanate groups.
  • a disadvantage of these polyisocyanates is that they require the addition of a photoinitiator for radiation curing with UV. If photoinitiators are added as separate components, this requires, on the one hand, an additional metering step and, on the other hand, entails the risk of incorrect metering. In addition, there is the risk with the dosed low molecular weight photoinitiators that they can migrate from the cured coating and so in case of use in UV curable inks for packaging can go on the contents.
  • the incorporable photoinitiators should contain no toxicologically harmful substances, the applicability thereof, for. in packaging for foodstuffs.
  • the reaction mixtures obtained in the preparation of the polyurethanes of the invention generally have a number average molecular weight M n of less than 10,000 g / mol, preferably less than 5000 g / mol, more preferably less than 4000 and most preferably less than 2000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the polyurethanes according to the invention have virtually no free isocyanate groups, i. the content of free isocyanate groups is less than 0.5% by weight, preferably less than 0.3, particularly preferably less than 0.2, very particularly preferably less than 0.1, in particular less than 0.05 and especially 0% by weight.
  • Component (a) comprises allophanate-containing polyisocyanates having an NCO functionality of at least 2, preferably from 2 to 5 and particularly preferably from 2 to 4.
  • the allophanate-containing polyisocyanates (a) are from aliphatic C 4 - to C 20 -alkylene diisocyanates built up, preferably from 1,6-hexamethylene diisocyanate.
  • Component (b) is particularly preferably bound to component (a) via allophanate groups.
  • the structural components at least 20 mol%, preferably at least 25 mol%, particularly preferably at least 30 mol%, very particularly preferably at least 35 mol%, in particular at least 40 mol% and especially at least 50 mol% of allophanate groups are bonded to the novel polyurethanes (A).
  • n is a positive number, which is 1 to 5 on average, preferably 1 to 3, on a statistical average.
  • Component (b) according to the invention is at least one compound (b) which carries at least one isocyanate-reactive group and at least one free-radically polymerizable group.
  • the compounds (b) preferably have exactly one isocyanate-reactive group and 1 to 5, more preferably 1 to 4 and most preferably 1 to 3 radically polymerizable groups.
  • the components (b) preferably have a molecular weight of below 10,000 g / mol, more preferably below 5000 g / mol, very preferably below 4000 g / mol and in particular below 3000 g / mol.
  • Specific compounds (b) have a molecular weight below 1000 or even below 600 g / mol.
  • Isocyanate-reactive groups can be, for example, -OH, -SH, -NH 2 and -NHR 1 , where R 1 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as, for example, methyl, ethyl, n-propyl, iso -propyl, n- Butyl, iso- butyl, sec- butyl or tert- butyl, means.
  • Components (b) may be, for example, monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid and methacrylamidoglycolic acid, which preferably have 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, Triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,2-, 1,3- or 1,4- Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-
  • esters or amides of (meth) acrylic acid with amino alcohols z.
  • unsaturated polyether or polyesterols or polyacrylate polyols having an average OH functionality of 2 to 10, although less preferred.
  • amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxymethylmethacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N-hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide or N-hydroxyalkylmaleimides such as N-hydroxyethylmaleimide.
  • hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxymethylmethacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N-hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide or N-hydroxyalkylmaleimides such as N-hydroxyethylmaleimide.
  • 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate, 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and the monoacrylates of polyethylene glycol of molecular weight from 106 to 238.
  • component (b) may also be technical mixtures of the acrylation of trimethylolpropane, pentaerythritol, ditrimethylolpropane or dipentaerythritol or alkoxylated, preferably propoxylated and / or ethoxylated, more preferably ethoxylated trimethylolpropane, pentaerythritol, ditrimethylolpropane or dipentaerythritol.
  • compounds (b) are technical mixtures of acrylation of pentaerythritol, which is usually a OH number according to DIN 53240 of 99 to 115 mg KOH / g and consist predominantly of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and may contain minor amounts of pentaerythritol diacrylate.
  • pentaerythritol tetraacrylate is not incorporated into the polyurethane according to the invention, but at the same time acts as a reactive diluent.
  • Component (c) is at least one photoinitiator having at least one isocyanate-reactive group, preferably at least one ⁇ -hydroxyacetophenone-type or benzophenone-type photoinitiator, each having at least one isocyanate-reactive group, more preferably at least one photoinitiator of ⁇ -hydroxyacetophenone type.
  • a photoinitiator is understood to be a compound which is capable of being cleaved by electromagnetic radiation, preferably by UV radiation, visible light or IR radiation, particularly preferably by UV radiation or visible light and very particularly preferably by UV radiation into at least one radical.
  • the component (c) may contain one or more than one, for example 1 to 3, preferably 1 to 2 and particularly particularly preferably one photoinitiator active group, preferably ⁇ -hydroxyacetophenone or benzophenone group, more preferably ⁇ -hydroxyacetophenone. Furthermore, component (c) may contain one or more than one, for example 1 to 4, preferably 1 to 3, more preferably 1 to 2 and most preferably exactly one isocyanate-reactive group.
  • the groups which are active as photoinitiator may preferably be hydroxybenzophenones or hydroxyacetophenones and more preferably hydroxyacetophenones.
  • the group -O - [- Y i -] p -H is in para position to the carbonyl group.
  • radicals R 3 , R 4 and R 5 are preferably independently of one another hydrogen or methyl, particularly preferably hydrogen.
  • p is 0 to 4, more preferably 1 to 3, and most preferably 1.
  • Preferred components (c) are 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexyl-phenylketone, 1- [4- [2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propane-1 on, 2-hydroxy-1- [4- [hydroxy- [4- (2-hydroxy-2-methylpropanoyl) phenyl] methyl] phenyl] -2-methylpropane-1-one, [4- [ 3- (4-benzoylphenoxy) -2-hydroxy-propoxy] -phenyl] -phenyl-methanone, Benzoin, benzoin iso-butyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether
  • Optional component (d) is at least one other di- and / or polyisocyanate other than compound (a).
  • diisocyanates are possible, i. Connections with the functionality 2.
  • Suitable components (d) are, for example, aliphatic, aromatic and cycloaliphatic diisocyanates and polyisocyanates having an NCO functionality of at least 2, preferably 2 to 5 and more preferably more than 2 to 4.
  • Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates of straight-chain or branched C 4 -C 20 -alkylene diisocyanates, cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.
  • isocyanurates, biurets and allophanates particularly preferably isocyanurates and allophanates and very particularly preferably allophanates.
  • the polyisocyanates are preferably polyisocyanates based on one or more diisocyanates having 4 to 20 carbon atoms.
  • diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane,
  • hexamethylene diisocyanate 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane, particularly preferably hexamethylene diisocyanate.
  • the polyisocyanates are composed of aliphatic and / or cycloaliphatic polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.
  • Suitable components (e) are compounds containing at least two isocyanate-reactive groups, for example -OH, -SH, -NH 2 or -NHR 2 , in which R 2 independently of one another is hydrogen, methyl, ethyl, isopropyl , n Propyl, n-butyl, iso -butyl, sec- butyl or tert -butyl.
  • Compounds (e) having exactly 2 isocyanate-reactive groups are preferably diols having 2 to 20 carbon atoms, for example ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol, 2-butyl 2-ethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 1,2-, 1,3- or 1,4-butanediol , 1,6-hexanediol, 1,10-decanediol, bis (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclohexanediol
  • cycloaliphatic diols e.g. Bis (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, cyclooctanediol or norbornanediol.
  • Other compounds (e) may be compounds having at least three isocyanate-reactive groups.
  • these components may have 3 to 6, preferably 3 to 5, more preferably 3 to 4 and most preferably 3 isocyanate-reactive groups.
  • the molecular weight of these components is generally not more than 2000 g / mol, preferably not more than 1500 g / mol, more preferably not more than 1000 g / mol and most preferably not more than 500 g / mol.
  • Optional components (f) are those with optionally at least one compound having exactly one isocyanate-reactive group. In a preferred embodiment, at least one component (f) is present.
  • Examples thereof are methanol, ethanol, isopropanol , n-propanol, n-butanol, isobutanol , sec- butanol, tert- butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, iso- decanol- Isomer mixtures, undecanol, n-dodecanol (lauryl alcohol), iso tridecanol isomer mixtures, n tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, 2-ethylhexanol, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecano
  • the monools may be the said cycloaliphatic alcohols, preferably cyclopentanol or cyclohexanol, more preferably cyclohexanol.
  • the monools can be the stated aliphatic alcohols having 6 to 20 carbon atoms, more preferably those having 8 to 20 carbon atoms, very particularly preferably those having 10 to 20 carbon atoms.
  • the monools are the aliphatic alcohols mentioned, very particularly preferably those having 1 to 4 carbon atoms, in particular ethanol.
  • the polyurethanes (A) When using such alkoxylated aliphatic alcohols as component (f) in the polyurethanes (A) according to the invention, the polyurethanes (A) thus obtainable show, in addition to their other positive properties, an improved dispersion of pigments in the inks and printing inks according to the invention, resulting in an increased color density in the printing process allows.
  • the polyurethanes which can be used according to the invention are obtained by reacting the components (a), (b) and (c) and optionally (d) and / or (e) and / or (f) with one another.
  • the formation of the adduct of isocyanate group-containing compound and the compound containing isocyanate-reactive groups is generally carried out by mixing the components in any order, optionally at elevated temperature.
  • the compound containing isocyanate-reactive groups is preferably added to the compound containing isocyanate groups, preferably in several steps.
  • the isocyanate group-containing compound (a) and optionally (d) and the compounds containing isocyanate-reactive groups added are initially charged and then (b) and / or (c), preferably (b), are added. Subsequently, optionally desired further components can be added.
  • reaction is carried out at temperatures between 5 and 100 ° C, preferably between 20 to 90 ° C and more preferably between 40 and 80 ° C and in particular between 60 and 80 ° C.
  • the process according to the invention is carried out in the presence of less than 1000 ppm by weight, preferably less than 500, more preferably less than 250 and very preferably less than 100 ppm by weight of a bismuth, zinc and / or titanium-containing compound a bismuth and / or titanium-containing compound, and more preferably a bismuth-containing compound.
  • Particularly preferred salts have as anions monocarboxylates of the general formula (C n H 2n-1 O 2 ) - , where n is the numbers 1 to 20.
  • the preferred zinc carboxylates are those of carboxylates which have at least six carbon atoms, very particularly preferably at least eight carbon atoms, in particular zinc (II) diacetate or zinc (II) dioctoate or zinc carbonate. (II) neodecanoate.
  • Commercially available catalysts are, for example, Borchi® Kat 22 from OMG Borchers GmbH, Langenfeld, Germany.
  • the bismuth carboxylates are preferred, more preferably those of carboxylates having at least six carbon atoms, especially bismuth octoates, ethyl hexanoates, neodecanoates, or pivalates; for example, K-KAT 348, XC-B221; XC-C227, XC 8203 and XK-601 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals and those from Shepherd Lausanne, and, for example, Borchi® Kat 24; 315; 320 from OMG Borchers GmbH, Langenfeld, Germany.
  • the titanium tetra-alcoholates Ti (OR) 4 are preferred, more preferably those of alcohols ROH having 1 to 8 carbon atoms, for example, methanol, ethanol, iso -propanol, n-propanol, n-butanol, iso -butanol, sec Butanol, tert- butanol, n-hexanol, n-heptanol, n-octanol, are preferably methanol, ethanol, iso -propanol, n-propanol, n-butanol, tert -butanol, particularly preferably isopropanol and n- butanol.
  • alcohols ROH having 1 to 8 carbon atoms for example, methanol, ethanol, iso -propanol, n-propanol, n-butanol, iso -butanol, sec Butanol, tert
  • Anhydrous here means that the water content in the reaction system is not more than 5% by weight, preferably not more than 3% by weight and particularly preferably not more than 1% by weight, very particularly preferably not more than 0.75 and in particular not more than 0, 5% by weight. If not worked anhydrous there is a risk that under the reaction conditions water reacts with the free isocyanate groups and cause the forming amino groups side reaction, for example, a Michael addition to (meth) acrylate or react with other free isocyanate groups to poorly soluble biurets.
  • the reaction is carried out in the presence of at least one oxygen-containing gas, e.g. Air or air-nitrogen mixtures or mixtures of oxygen or an oxygen-containing gas with an inert gas under the reaction conditions, which have an oxygen content of less than 15, preferably less than 12, more preferably less than 10, most preferably less than 8 and in particular less than 6 vol% ,
  • at least one oxygen-containing gas e.g. Air or air-nitrogen mixtures or mixtures of oxygen or an oxygen-containing gas with an inert gas under the reaction conditions, which have an oxygen content of less than 15, preferably less than 12, more preferably less than 10, most preferably less than 8 and in particular less than 6 vol% ,
  • the reaction mixture is up to 1000 Gew.ppm added to at least one process stabilizer.
  • Preferred process stabilizers are phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl and quinone methides.
  • the reaction of the isocyanate group-containing compound (a) or the reaction product of (a) and (b) with the compound (C) carried out by using the isocyanate group-containing compound in an excess of NCO groups based on the isocyanate-reactive groups in (c) of at least 20 mol%.
  • This has the consequence that the compounds (c) react substantially completely.
  • the excess of isocyanate groups can then be reacted with further compound (b) and / or compound (f), preferably with compound (f).
  • the reaction may also be carried out in the presence of an inert solvent, such as acetone, iso-butyl-methyl ketone, toluene, xylene, butyl acetate, methoxypropyl acetate or ethoxyethyl acetate.
  • an inert solvent such as acetone, iso-butyl-methyl ketone, toluene, xylene, butyl acetate, methoxypropyl acetate or ethoxyethyl acetate.
  • the reaction is carried out in the absence of a solvent.
  • reaction of (a) with (b) and / or (c), preferably (a) and (b) is carried out under allophanatization conditions.
  • allophanatization conditions are to be understood as meaning reaction conditions under which allophanate groups are formed at least in part, preferably those reaction conditions under which more isocyanate groups of various competing reactions of the isocyanate groups react to form allophanate groups than to other reaction products.
  • such compounds are used as in the WO 00/39183 , P.4, Z. 3 to p. 10, Z. 19, the disclosure of which is herewith part of the present document.
  • Particularly preferred among these are those compounds which have as structural components at least one (cyclo) aliphatic isocyanate containing allophanate groups and at least one hydroxyalkyl (meth) acrylate, very particularly preferably the product Nos. 1 to 9 in Table 1 on page 24 of the WO 00/39183 , Very particular preference is given to those polyisocyanates of the formula (I) described above.
  • the content of water is preferably at least 0.75% by weight, more preferably at least 1% by weight, most preferably at least 1.25% by weight and in particular at least 1.5% by weight, based on the amount of polyurethane (A).
  • the content of water is preferably up to 3.5% by weight, more preferably up to 3% by weight, based on the amount of polyurethane (A).
  • the viscosity of the polyurethane (A) can be reduced by adding said amount of water.
  • the viscosity measured in accordance with DIN EN ISO 3219 (shear rate D, 100 s -1 ) at 23 ° C. is not more than 400 Pas, so that the formulation is free-flowing.
  • the viscosity is preferably less than 300, more preferably less than 250 Pas and most preferably less than 200 Pas.
  • the formulation may be in the form of a solution or dispersion, preferably as a solution of water in the polyurethane (A).
  • the amount of water is optionally added in portions in the polyurethane (A) with input of energy.
  • the polyurethane (A) is added to water.
  • the mixing can be carried out, for example, by stirring, static mixers or ultrasound, preferably by stirring.
  • polyurethanes (A) and the formulations of incorporable photoinitiators according to the invention can preferably be used in inks, printing inks and printing varnishes according to the invention.
  • the printing lacquers of the invention contain no pigment.
  • the at least one further photoinitiator is preferably present in pigmented printing inks and printing inks.
  • printing ink is used in this application as a collective name for colorant-containing preparations with different consistency, which are transferred exclusively by means of a printing plate on a substrate and there fixed as a color film (pressure) (CEPE definition).
  • ink ink jet ink liquid liquids and liquid toner for electrophotographic printing processes.
  • the inks, printing inks and printing varnishes according to the invention can be used for printing on various substrates, preferably polyamides, polyethylene, polypropylene, polyesters, polyethylene terephthalate, polystyrene, paper, cardboard, cardboard, plastic-coated paper, plastic-coated cardboard or plastic-coated cardboard, aluminum and aluminum-coated plastic films of polyethylene, polypropylene and polyesters as well as paper and cardboard
  • the plastic is preferably polyolefins, more preferably polyethylene or polypropylene.
  • the substrates thus printed are particularly suitable as packaging materials for food, cosmetics and pharmaceuticals.
  • the polyurethanes (A) according to the invention can be used as the sole binder or, preferably, in combination with at least one further free-radically polymerizable compound.
  • Radical polymerizable groups are for example preferred (meth) acrylate groups and more preferably acrylate groups.
  • the free-radically polymerizable compounds (B) are preferably polyfunctional compounds (compounds having more than one free-radically polymerizable double bond) that can be polymerized.
  • (Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.
  • Multifunctional, polymerizable compounds are preferably multifunctional (meth) acrylates which carry at least 2, preferably 2-10, more preferably 3-6 and most preferably 3-4 (meth) acrylate groups, preferably acrylate groups.
  • Examples of multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate , Neopentyl glycol diacrylate, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol diacrylate, 1,2-, 1,3- or 1,4-cyclohexanediol diacrylate, diproypline glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentahacrylate.
  • sugar alcohols such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol ( Galactitol), maltitol or isomalt, or of polyester polyols, polyetherols, poly-THF with a Molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between 134 and 1178, polyethylene glycol with a molecular weight between 106 and 898, and also epoxy (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, Urethane (meth) acrylates or polycarbonate
  • sugar alcohols such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribito
  • C 1 -C 18 -alkyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl Methyl, ethyl or n-propyl, most preferably methyl or ethyl.
  • Preferred multifunctional, polymerizable compounds are 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, diproypline glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylol tetracrylate and dipentaerythritol hexaacrylate, polyester polyol acrylates, polyetherol acrylates and triacrylate of one to twenty times alkoxylated, more preferably one to twenty times ethoxylated trimethylolpropane, one to 20 times propoxylated glycerol or one to 20 times ethoxylated and / or propoxylated pentaerythritol.
  • epoxy (meth) acrylates are used as multifunctional, polymerizable compounds in printing finishes.
  • Very particularly preferred multifunctional, polymerizable compounds are trimethylolpropane triacrylate and triacrylate of one to twenty times ethoxylated trimethylolpropane, triacrylate of one to 20 times propoxylated glycerol or tetraacrylate of one to 20 times ethoxylated and / or propoxylated pentaerythritol. Further constituents may also be partially or completely esterified with (meth) acrylic acid esterified polyalcohols.
  • Such polyalcohols are, for example, at least divalent polyols, polyetherols or polyesterols or polyacrylate polyols having an average OH functionality of at least 2, preferably at least 3, more preferably at least 4 and most preferably 4 to 20.
  • Polyetherols in addition to the alkoxylated polyols also polyethylene glycol having a molecular weight between 106 and 2000, polypropylene glycol having a molecular weight between 134 and 2000, poly-THF having a molecular weight between 162 and 2000 or poly-1,3-propanediol having a molecular weight between 134 and 400 be.
  • Polyester polyols are, for example Ullmanns Encyklopadie der ischen Chemie, 4th Edition, Volume 19, pp. 62 to 65 known. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids to be obtained. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples include:
  • anhydrides or dialkyl esters for example C 1 -C 4 alkyl esters,
  • dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • Suitable polyhydric alcohols for the preparation of the polyesterols are 1,2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, polyethylene glycol having a molecular weight between 106 and 2000 , Polypropylene glycol having a molecular weight between 134 and 2000, poly-THF having a molecular weight between 162 and 2000, poly-1,3-propanediol having a molecular weight between 134 and 400, neopentyl glycol, neopentyl glycol hydroxy
  • Alcohols of the general formula HO- (CH 2 ) x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20, are preferred.
  • Preferred are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Further preferred is neopentyl glycol.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
  • Preferred lactones are those which are derived from compounds of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit may also be substituted by a C 1 - to C 4 -alkyl radical.
  • Examples are ⁇ -caprolactone, ⁇ -propiolactone, gamma-butyrolactone and / or methyl- ⁇ -caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and mixtures thereof.
  • Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • polycarbonate diols e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.
  • the multifunctional, polymerizable compound may be urethane (meth) acrylates, epoxy (meth) acrylates or carbonate (meth) acrylates.
  • Urethane (meth) acrylates are e.g. obtainable by reacting polyisocyanates with hydroxyalkyl (meth) acrylates and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.
  • chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.
  • urethane (meth) acrylates dispersible in water without the addition of emulsifiers additionally contain ionic and / or nonionic hydrophilic groups which are present, for example. be incorporated by structural components such as hydroxycarboxylic acids in the urethane.
  • the components (1), (2) and (3) may be the same as described above as structural components (a), (b) and (e) for the polyurethanes of the invention.
  • the urethane (meth) acrylates preferably have a number average molecular weight M n from 500 to 20,000, in particular 500 to 10000 more preferably 600 to 3000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably 2 to 4 moles of (meth) acrylic groups per 1000 g of urethane (meth) acrylate.
  • Epoxy (meth) acrylates are obtainable by reacting epoxides with (meth) acrylic acid.
  • Suitable epoxides are, for example, epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.
  • Epoxidized olefins may be, for example, ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, vinyl oxirane, styrene oxide or epichlorohydrin.
  • Preferred are ethylene oxide, propylene oxide, isobutylene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, particularly preferably ethylene oxide, propylene oxide or epichlorohydrin and most preferably ethylene oxide and epichlorohydrin.
  • Aromatic glycidyl ethers are e.g. Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, e.g. 2,5-bis [(2,3-E-poxypropoxy) phenyl] octahydro-4,7-methano-5H-indene (CAS No. [13446-85-0]), tris [4- (2, 3-epoxypropoxy) phenyl] methane isomers) CAS-No. [66072-39-7]), phenol based epoxy novolacs (CAS # [9003-35-4]) and cresol based epoxy novolacs (CAS # [37382-79-9]).
  • Bisphenol A diglycidyl ether bisphenol F diglycidyl ether
  • Aliphatic glycidyl ethers are, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane (CAS No. [27043] 37-4]), diglycidyl ethers of polypropylene glycol ( ⁇ , ⁇ -bis (2,3-epoxypropoxy) poly (oxypropylene) (CAS No. [16096-30-3]) and hydrogenated bisphenol A (2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, CAS No. [13410-58-7]).
  • the epoxide (meth) acrylates preferably have a number-average molecular weight M n of from 200 to 20 000, particularly preferably from 200 to 10 000 g / mol and very particularly preferably from 250 to 3000 g / mol; the content of (meth) acrylic groups is preferably 1 to 5, more preferably 2 to 4 per 1000 g of epoxy (meth) acrylate (determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).
  • carbonate (meth) acrylates preferably contain 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.
  • the number average molecular weight M n of the carbonate (meth) acrylates is preferably less than 3000 g / mol, more preferably less than 1500 g / mol, more preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).
  • the carbonate (meth) acrylates are obtainable in a simple manner by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, eg hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or else transesterification with (meth) acrylic esters, such as it eg in EP-A 92 269 is described. They are also available by reacting phosgene, urea derivatives with polyhydric, for example dihydric alcohols.
  • (meth) acrylates of polycarbonate polyols such as the reaction product of one of said diols or polyols and a carbonic acid ester and a hydroxyl-containing (meth) acrylate.
  • Suitable carbonic acid esters are e.g. Ethylene, 1,2 or 1,3-propylene carbonate, carbonic acid dimethyl, diethyl or dibutyl ester.
  • Suitable hydroxyl-containing (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth ) acrylate, trimethylolpropane mono- and di (meth) acrylate and pentaerythritol mono-, di- and tri (meth) acrylate.
  • Particularly preferred carbonate (meth) acrylates are those of the formula: wherein R is H or CH 3 , X is a C 2 -C 18 alkylene group and n is an integer from 1 to 5, preferably 1 to 3.
  • R is preferably H and X is preferably C 2 -C 10 -alkylene, for example 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene or 1,6-hexylene, particularly preferred for C 4 - to C 8 -alkylene. Most preferably, X is C 6 alkylene.
  • the carbonate (meth) acrylates are aliphatic carbonate (meth) acrylates.
  • urethane (meth) acrylates are particularly preferred.
  • photoinitiator to the inks, printing inks and printing varnishes according to the invention in addition to the polyurethane (A), preferably a photoinitiator which has a different absorption maximum than component (c).
  • Photoinitiators may be, for example, photoinitiators known to the person skilled in the art, for example those in “ Advances in Polymer Science “, Volume 14, Springer Berlin 1974 or in KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3 ; Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London s.
  • Suitable examples include mono- or Bisacylphosphinoxide, as they are eg in EP-A 7 508 .
  • EP-A 495 751 or EP-A 615 980 For example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO from BASF SE), ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin® TPO L from BASF SE), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure® 819 from BASF SE), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and its derivatives or mixtures of these photoinitiators.
  • 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO from BASF SE)
  • Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, ⁇ -methylanthraquinone , tert -butylanthraquinone, anthraquinone carboxylic acid ester, benzaldehyde, ⁇ -tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone
  • photoinitiators are polymeric photoinitiators, such as, for example, the diester of carboxymethoxybenzophenone with polytetramethylene glycols of different molecular weight, preferably 200 to 250 g / mol ( CAS 515136-48-8 ), such as CAS 1246194-73-9 . CAS 813452-37-8 . CAS 71512-90-8 . CAS 886463-10-1 or other polymeric benzophenone derivatives, such as those commercially available, for example, under the trade name Omnipol® BP from IGM Resins BV, Waalwijk, Netherlands or Genopol® BP1 from Rahn AG, Switzerland.
  • polymeric photoinitiators such as, for example, the diester of carboxymethoxybenzophenone with polytetramethylene glycols of different molecular weight, preferably 200 to 250 g / mol ( CAS 515136-48-8 ), such as CAS 1246194-73-9 . CAS 8
  • polymeric thioxanthones for example the diesters of carboxymethoxythioxanthones with polytetramethylene glycols of different molecular weight, such as are commercially available, for example, under the trade name Omnipol® TX from IGM Resins BV, Waalwijk, the Netherlands.
  • polymeric ⁇ -aminoketones for example the diesters of carboxyethoxythioxanthones with polyethylene glycols of different molecular weight, such as are commercially available, for example, under the trade name Omnipol® 910 or Omnipol® 9210 from IGM Resins BV, Waalwijk, the Netherlands.
  • silsesquioxane compounds having at least one initiating group as described are used as photoinitiators WO 2010/063612 A1 there especially from page 2, line 21 to page 43, line 9, which is hereby incorporated by reference into the present disclosure, preferably from page 2, line 21 to page 30, line 5 and in the examples of WO 2010/063612 A1 described compounds.
  • Non- or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type as in DE-A 198 26 712 .
  • DE-A 199 13 353 or WO 98/33761 described silsesquioxane compounds.
  • photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, 2- (Dimethylamino) -1- (4-morpholinophenyl) -2- (p-tolylmethyl) butan-1-one, 2-hydroxy-1- [4 - [[4- (2-hydroxy-2-methylpropanoyl ) phenyl] methyl] phenyl] -2-methyl-propan-1-one and the above-described polymeric thioxanthone and benzophenone derivatives and the in WO 2010/063612 A1 described.
  • additives for printing inks for example dispersants, waxes, stabilizers, sensitizers, fillers, defoamers, dyes, antistatic agents, thickeners, surface-active agents such as leveling agents, slip aids or adhesion promoters can be used.
  • Suitable fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.
  • silicates e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.
  • Preferred pigments (B) are monoazo pigments (especially laked BONS pigments, Naphthol AS pigments), disazo pigments (especially diaryl, Bisacetessigklareacetanilidpigmente, disazo pyrazolone pigments), quinacridone pigments, quinophthalone pigments, perinone pigments, phthalocyanine pigments, triarylcarbonium (alkali blue pigments, laked rhodamines, dye salts with complex Anions), isoindoline pigments, white pigments and carbon blacks.
  • monoazo pigments especially laked BONS pigments, Naphthol AS pigments
  • disazo pigments especially diaryl, Bisacetessigklacetanilidpigmente, disazo pyrazolone pigments
  • quinacridone pigments quinophthalone pigments, perinone pigments, phthalocyanine pigments, triarylcarbonium (alkali blue pigments, laked rhodamines, dye salts with complex Anions), isoin
  • pigments are: carbon black, titanium dioxide, C.I. Pigment Yellow 138, C.I. Pigment Red 122 and 146, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43 and C.I. Pigment Green 7.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin® brands from BASF) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate, or quinone methides (such as Irgastab® UV 22) are used. Stabilizers are usually used in amounts of 0.1 to 0.5 wt .-%, the active ingredient component, based on the preparation.
  • suitable radical scavengers for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof,
  • Another aspect of the present invention is a method for printing flat or three-dimensional, preferably sheet-like substrates by any printing method using at least one printing ink according to the invention.
  • at least one printing ink according to the invention is printed on a substrate and then treated with actinic radiation, for example UV radiation and / or electron beams, preferably UV radiation.
  • Printing processes in which the printing inks according to the invention can be used are preferably offset printing, high-pressure, flexographic printing, gravure printing, screen printing and ink-jet printing. Particular preference is given to flexographic printing and offset printing.
  • UV-curable printing inks for these applications usually include reactive diluents, binders, colorants, initiators and optionally various additives. Binders serve to form the color film and anchor the constituents such as pigments or fillers in the paint film. Depending on the consistency, printing inks for these applications usually contain between 10 and 60% by weight of binder. Reactive diluents are used to adjust the processing viscosity.
  • Printing varnishes are either applied to the substrate as a primer (so-called “primer”) or applied to the printed substrate after the printing process as a coating.
  • Printing lacquers are used, for example, to protect the printed image, to improve the adhesion of the printing ink to the printing substrate or for aesthetic purposes.
  • the application is usually carried out in-line or offline by means of a coating unit on the printing press.
  • Print varnishes do not contain a colorant but, apart from that, are generally similar in composition to printing inks and are distinguished by the absence of the colorant.
  • Printing inks for mechanical printing include so-called pasty inks of high viscosity for offset and high pressure as well as so-called liquid inks of comparatively low viscosity for flexographic and gravure printing.
  • the inks according to the invention can be used, for example, as ink-jet liquid and for liquid toner for electrophotographic printing processes.
  • drying and / or radiation curing take place after each printing operation.
  • Radiation curing is performed with high energy light, e.g. UV light or electron beams.
  • the radiation curing can also be carried out at higher temperatures.
  • Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, impulse lamps, metal halide, electronic flash devices, which radiation curing without photoinitiator is possible, or Excimerstrahler and UV LEDs.
  • the radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps, UV LEDs or excimer radiators.
  • the radiation dose for UV curing which is usually sufficient for crosslinking, is in the range from 30 to 3000 mJ / cm 2 .
  • radiation sources can be used for the curing, e.g. two to four.
  • the irradiation may optionally also in the absence of oxygen, for. B. under inert gas atmosphere, are performed.
  • inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases.
  • Laromer ® LR 8863 from BASF SE, Ludwigshafen, Germany, is a commercially available triacrylate of 3.5 times ethoxylated trimethylolpropane statistical average.
  • Laromer® 9000 from BASF SE, Ludwigshafen, is a commercially available, allophanate-containing polyisocyanate of the above formula (I) in which acrylate groups are bonded via allophanate groups.
  • the NCO content is 14.5 to 15.5% by weight.
  • Irgacure ® 2959 from BASF SE, Ludwigshafen, Germany, is a commercially available photoinitiator from ⁇ -hydroxy ketone type (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane 1-one).
  • Irgastab UV22 ® from BASF SE, Ludwigshafen, Germany, is a commercially available stabilizer quinone dissolved in an acrylate of propoxylated glycerin.
  • Comparative Example 1 shows that it is necessary to react with a component (f) the free NCO groups.
  • Comparative Example 2 shows that the formulations according to the invention cloud on addition of too much water.
  • Example 2 A product was prepared analogously to Example 1 as a 70 wt% solution in Laromer ® LR 8863 without the addition of water and mixed with various amounts of water and the appearance and the viscosity tested. Viscosity at 25 ° C Fluidity at 25 ° C Miscibility Without 600 pas No Clear 1% water 322 pas Bad Clear 2% water 170 pas Well Clear 5% water 82 pas Very well cloudy
  • Example 5 from DE 10 2006 047863 was repeated and considered based on the photoinitiator content as a pure initiator (Comparison a) or based on its content of reactive diluents as a coating composition (Comparison c).
  • the formulations were used to determine the rate of cure, the viscosity, the gloss and the abrasion stability, and also the solvent resistance.
  • the varnish was coated with a 6 ⁇ m spiral blade on Leneta cardboard and exposed with a UV-system M-30-2x1-BLKU of the company IST, which is equipped with an adjustable 200W / cm Hg medium pressure lamp. The rate of cure was determined with the fingernail. If the surface had no scratches, the paint was considered hardened.
  • example 5 is DE 10 2006 047863 in direct comparison with the example according to the invention has poorer application properties, such as a lower residual gloss and lower abrasion resistance and shows insufficient reactivity.
  • Example 5 in Example 9a
  • Example 6 in Example 9b
  • Irgacure® 2959 was chosen.
  • concentration of Irgacure® 2959 in the comparative example corresponded to the concentration of the chromophore in the photoinitiator according to the invention.
  • all components were mixed and dispersed on a laboratory lathe Fa. Buhler until all photoinitiators were dissolved.
  • the printing ink was then printed on a coated cardboard with an application weight of 1.7 g / m 2 using an offset proofing device from the firm of für fürbau and exposed to an UV exposure unit M-30-2x1-BLKU from the company IST at 80 W / cm (aluminum reflectors).
  • the hardening was determined with the REL tester (PTC test device, Fa. fürbau).
  • the color density was determined using a densitometer SPM55 from Gretag-Macbeth.
  • the initiators according to the invention even have a significantly higher curing rate than the comparative example at the same chromophore concentration.
  • the color density as a measure of the intensity of the color impression is even higher in Example 9b, in which a fatty acid alcohol was used, than in the other experiments, which also indicates a dispersing effect of the photoinitiator according to the invention.

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Description

Die Erfindung betrifft niedrigviskose Formulierungen strahlungshärtbarer Verbindungen, Verfahren zu deren Herstellung, deren Verwendung und diese enthaltende Tinten, Druckfarben und Drucklacke.The invention relates to low-viscosity formulations of radiation-curable compounds, processes for their preparation, their use and inks containing them, printing inks and printing varnishes.

US 3429852 , US 3214492 , US 3622848 , US 4304895 offenbaren Aceto- und Benzophenonderivate als Photoinitiatoren, die, gegebenenfalls über eine Spacergruppe, mit einer (Meth)Acrylatgruppe verbunden sind und die somit bei einer radikalischen Polymerisation einbaubar sind. US 3,429,852 . US 3214492 . US 3622848 . US 4304895 disclose aceto and benzophenone derivatives as photoinitiators which, if appropriate via a spacer group, are bonded to a (meth) acrylate group and which can thus be incorporated in a free-radical polymerization.

DE 19501025 offenbart an Photoinitiatorsysteme gebundene Vinyloxycarbonylgruppen, die bei einer radikalischen Polymerisation ebenfalls einbaubar sind. DE 19501025 discloses vinyloxycarbonyl groups attached to photoinitiator systems which are also incorporatable in a free-radical polymerization.

Die dort offenbarten Verbindungen sind jedoch aufgrund der beschränkten Möglichkeiten der Spacerstrukturen nur in geringen Grenzen variabel. Außerdem werden solche Verbindungen oft nicht vollständig bei der UV -Polymerisation umgesetzt und können infolgedessen aus der Beschichtung migrieren.However, the compounds disclosed there are variable only within narrow limits due to the limited possibilities of the spacer structures. In addition, such compounds are often not fully reacted in UV polymerization and, as a result, can migrate out of the coating.

WO 03/68785 offenbart Umsetzungen von Photoinitiatoren des Acylphosphinoxid-Typs mit Diisocyanaten. Weitergehende Funktionalisierung der freien Isocyanatgruppen wird nicht offenbart. WO 03/68785 discloses reactions of acylphosphine oxide type photoinitiators with diisocyanates. Further functionalization of the free isocyanate groups is not disclosed.

WO 03/68783 offenbart Umsetzungen von gegebenenfalls hydroxyalkylierten Acylphosphinoxid-Photoinitiatoren mit Di- und Polyisocyanaten. Weitergehende Funktionalisierung der freien Isocyanatgruppen wird nicht offenbart. WO 03/68783 discloses reactions of optionally hydroxyalkylated acylphosphine oxide photoinitiators with di- and polyisocyanates. Further functionalization of the free isocyanate groups is not disclosed.

EP 632329 offenbart Photoinitiatoren vom Benzophenon-, Acetophenon- oder Hydroxyacetophenontyp, die mit Diisocyanaten funktionalisiert werden. Die so erhaltenen Isocyanate können anschließend weiter derivatisiert werden, beispielsweise durch Umsetzung der freien Isocyanatgruppe mit Hydroxyalkyl(meth)acrylaten, so daß Photoinitiatoren erhalten werden, die bei einer radikalischen Polymerisation einbaubar sind. EP 632329 discloses benzophenone, acetophenone or hydroxyacetophenone type photoinitiators which are functionalized with diisocyanates. The isocyanates thus obtained can then be further derivatized, for example by reacting the free isocyanate group with hydroxyalkyl (meth) acrylates, so that photoinitiators are obtained which can be incorporated in a free-radical polymerization.

Nachteilig an dieser Funktionalisierung ist, daß man durch den Einsatz von Diisocyanaten lediglich einen geringen Funktionalisierungsgrad erzielen kann.A disadvantage of this functionalization is that one can only achieve a low degree of functionalization by the use of diisocyanates.

DE 10 2006 047 863 A1 beschreibt die Anbindung von Photoinitiatoren an Polyisocyanate um diese einbaubar zu gestalten. DE 10 2006 047 863 A1 describes the attachment of photoinitiators to polyisocyanates to make them installable.

Nachteilig ist, daß die so entstehenden Produkte noch eine relativ hohe Viskosität aufweisen, was ihre Einarbeitbarkeit und Vielseitigkeit in Beschichtungsmassen und insbesondere Druckfarben und Drucklacken erschwert. Zudem werden ausschließlich Herstellungsbeispiele unter Verwendung von Dibutylzinndilaurat offenbart, das toxikologisch bedenklich ist.The disadvantage is that the resulting products still have a relatively high viscosity, which their incorporation and versatility in coating materials and in particular Printing inks and printing inks difficult. In addition, only manufacturing examples using dibutyltin dilaurate are disclosed, which is toxicologically questionable.

WO 00/39183 beschreibt allophanatgruppenhaltige Polyisocyanate, die radikalisch polymerisierbare, aktivierte C=C-Doppelbindungen tragen. WO 00/39183 describes allophanate-containing polyisocyanates which carry free-radically polymerizable, activated C = C double bonds.

DE 102 46 512 beschreibt ein unterschiedliches Verfahren zur Herstellung der gleichen Verbindungen wie in WO 00/39183 beschrieben, sowie unterschiedliche Folgeprodukte dieser Verbindungen. Offenbart wird auch die chemische Kopplung von Polymerisationsstabilisatoren über freie Isocyanatgruppen. DE 102 46 512 describes a different process for preparing the same compounds as in WO 00/39183 described, as well as different secondary products of these compounds. Also disclosed is the chemical coupling of polymerization stabilizers via free isocyanate groups.

Nachteilig an diesen Polyisocyanaten ist, daß sie zur Strahlungshärtung mit UV die Zugabe eines Photoinitiators erfordern. Werden Photoinitiatoren als gesonderte Komponenten zugegeben, so erfordert dies zum einen einen zusätzlichen Dosierschritt und bringt zum anderen die Gefahr einer Fehldosierung mit sich. Außerdem besteht bei den zudosierten niedermolekularen Photoinitiatoren die Gefahr, dass diese aus der gehärteten Beschichtung migrieren können und so im Falle der Anwendung in UV härtbaren Druckfarben für Verpackungen auf das Füllgut übergehen können.A disadvantage of these polyisocyanates is that they require the addition of a photoinitiator for radiation curing with UV. If photoinitiators are added as separate components, this requires, on the one hand, an additional metering step and, on the other hand, entails the risk of incorrect metering. In addition, there is the risk with the dosed low molecular weight photoinitiators that they can migrate from the cured coating and so in case of use in UV curable inks for packaging can go on the contents.

Aufgabe der vorliegenden Erfindung war es, Photoinitiatoren zur Verfügung zu stellen, die in strahlungshärtbaren Beschichtungsmassen und besonders Tinten, Druckfarben und Drucklacken möglichst vollständig einbaubar sind und ein geringere Migrationstendenz zeigen und dabei eine niedrigere Viskosität aufweisen als vergleichbare Produkte aus dem Stand der Technik. Zudem sollen die einbaubaren Photoinitiatoren keine toxikologisch bedenklichen Stoffe enthalten, die deren Anwendbarkeit z.B. in Verpackungen für Lebensmittel entgegenstehen.It was an object of the present invention to provide photoinitiators which are as completely as possible to be incorporated in radiation-curable coating compositions and in particular inks, printing inks and printing lacquers and show a lower migration tendency and have a lower viscosity than comparable products of the prior art. In addition, the incorporable photoinitiators should contain no toxicologically harmful substances, the applicability thereof, for. in packaging for foodstuffs.

Die Aufgabe wurde gelöst durch ein Verfahren zur Herstellung von einbaubaren Photoinitiatoren mit niedriger Viskosität, umfassend die Schritte

  1. 1) Aufbau eines Polyurethans A, enthaltend als Aufbaukomponenten
    1. (a) mindestens ein allophanatgruppenhaltiges Polyisocyanat mit einer NCO Funktionalität von mindestens 2, aufgebaut aus aliphatischen C4- bis C20-Alkylendiisocyanaten,
    2. (b) mindestens eine Verbindung mit jeweils mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren ungesättigten Gruppe,
    3. (c) mindestens einen Photoinitiator mit mindestens einer gegenüber Isocyanat reaktiven Gruppe,
    4. (d) gegebenenfalls mindestens ein weiteres Di- und/oder Polyisocyanat, das von der Verbindung (a) verschieden ist,
    5. (e) gegebenenfalls mindestens eine Verbindung mit mindestens zwei gegenüber Isocyanat reaktiven Gruppen, sowie
    6. (f) gegebenenfalls mindestens eine Verbindung mit genau einer gegenüber Isocyanat reaktiven Gruppe
unter wasserfreien Bedingungen, wobei die Herstellung der Polyurethane (A) in Gegenwart von weniger als 1000 Gew. ppm einer Wismut-, Zink- und/oder Titan-haltigen Verbindung erfolgt und man in einem Schritt 2) das aus Schritt 1) erhaltene Polyurethan (A) mit 0,5 bis 4 Gew% Wasser, bezogen auf die Menge Polyurethan (A), vermischt.The object has been achieved by a process for the preparation of incorporable low viscosity photoinitiators comprising the steps
  1. 1) Structure of a polyurethane A, containing as structural components
    1. (a) at least one allophanate-containing polyisocyanate having an NCO functionality of at least 2, composed of aliphatic C 4 -C 20 -alkylene diisocyanates,
    2. (b) at least one compound having in each case at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group,
    3. (c) at least one photoinitiator having at least one isocyanate-reactive group,
    4. (d) optionally, at least one further di- and / or polyisocyanate other than compound (a),
    5. (E) optionally at least one compound having at least two isocyanate-reactive groups, and
    6. (f) optionally at least one compound having exactly one isocyanate-reactive group
under anhydrous conditions, the polyurethanes (A) being prepared in the presence of less than 1000 ppm by weight of a bismuth, zinc and / or titanium-containing compound, and in a step 2) the polyurethane obtained from step 1) A) with 0.5 to 4% by weight of water, based on the amount of polyurethane (A), mixed.

Die bei der Herstellung der erfindungsgemäßen Polyurethane erhaltenen Reaktionsgemische weisen in der Regel ein zahlenmittleres Molgewicht Mn von weniger als 10000 g/mol, bevorzugt von weniger als 5000 g/mol, besonders bevorzugt von weniger als 4000 und ganz besonders bevorzugt von weniger als 2000 g/mol (bestimmt durch Gelpermeationschromatographie mit Tetrahydrofuran und Polystyrol als Standard) auf.The reaction mixtures obtained in the preparation of the polyurethanes of the invention generally have a number average molecular weight M n of less than 10,000 g / mol, preferably less than 5000 g / mol, more preferably less than 4000 and most preferably less than 2000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

In einer bevorzugten Ausführungsform der Erfindung weisen die erfindungsgemäßen Polyurethane praktisch keine freien Isocyanatgruppen mehr auf, d.h. der Gehalt an freien Isocyanatgruppen beträgt weniger als 0,5 Gew%, bevorzugt weniger als 0,3, besonders bevorzugt weniger als 0,2, ganz besonders bevorzugt weniger als 0,1, insbesondere weniger als 0,05 und speziell 0 Gew%.In a preferred embodiment of the invention, the polyurethanes according to the invention have virtually no free isocyanate groups, i. the content of free isocyanate groups is less than 0.5% by weight, preferably less than 0.3, particularly preferably less than 0.2, very particularly preferably less than 0.1, in particular less than 0.05 and especially 0% by weight.

Bei der Komponente (a) handelt es sich um allophanatgruppenhaltige Polyisocyanate mit einer NCO Funktionalität von mindestens 2, bevorzugt von 2 bis 5 und besonders bevorzugt von 2 bis 4. Die allophanatgruppenhaltigen Polyisocyanate (a) sind aus aliphatischen C4- bis C20-Alkylendiisocyanaten aufgebaut, bevorzugt aus 1,6-Hexamethylendiisocyanat.Component (a) comprises allophanate-containing polyisocyanates having an NCO functionality of at least 2, preferably from 2 to 5 and particularly preferably from 2 to 4. The allophanate-containing polyisocyanates (a) are from aliphatic C 4 - to C 20 -alkylene diisocyanates built up, preferably from 1,6-hexamethylene diisocyanate.

Besonders bevorzugt ist die Komponente (b) über Allophanatgruppen an die Komponente (a) gebunden.Component (b) is particularly preferably bound to component (a) via allophanate groups.

Erfindungsgemäß können die Polyurethane (A) Allophanatgruppen enthalten, bevorzugt beträgt der Gehalt an Allophanatgruppen bei derartigen erfindungsgemäßen Polyurethanen (berechnet als C2N2HO3 = 101 g/mol) 1 bis 28 Gew%, bevorzugt von 3 bis 25 Gew%.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind von den Verbindungen (b) mit jeweils mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren ungesättigten Gruppe, die Aufbaukomponenten der erfindungsgemäßen Polyurethane (A) bilden, mindestens 20 mol%, bevorzugt mindestens 25 mol%, besonders bevorzugt mindestens 30 mol%, ganz besonders bevorzugt mindestens 35 mol%, insbesondere mindestens 40 mol% und speziell mindestens 50 mol% an Allophanatgruppen gebunden.According to the invention, the polyurethanes (A) may contain allophanate groups; the content of allophanate groups in such polyurethanes of the invention (calculated as C 2 N 2 HO 3 = 101 g / mol) is preferably from 1 to 28% by weight, preferably from 3 to 25% by weight.
In a preferred embodiment of the present invention, of the compounds (b) each having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group, the structural components at least 20 mol%, preferably at least 25 mol%, particularly preferably at least 30 mol%, very particularly preferably at least 35 mol%, in particular at least 40 mol% and especially at least 50 mol% of allophanate groups are bonded to the novel polyurethanes (A).

In einer besonders bevorzugten Ausführungsform handelt es sich um ein allophanatgruppenhaltiges Polyisocyanat der Formel (I)

Figure imgb0001
worin n eine positive Zahl ist, die im statistischen Mittel 1 bis zu 5, bevorzugt von 1 bis 3 beträgt.In a particularly preferred embodiment, it is an allophanate-containing polyisocyanate of the formula (I)
Figure imgb0001
 wherein n is a positive number, which is 1 to 5 on average, preferably 1 to 3, on a statistical average.

Als Komponente (b) kommen erfindungsgemäß mindestens eine Verbindung (b) in Betracht, die mindestens eine gegenüber Isocyanat reaktive Gruppe und mindestens eine radikalisch polymerisierbare Gruppe trägt.Component (b) according to the invention is at least one compound (b) which carries at least one isocyanate-reactive group and at least one free-radically polymerizable group.

Die Verbindungen (b) weisen bevorzugt genau eine gegenüber Isocyanat reaktive Gruppe auf und 1 bis 5, besonders bevorzugt 1 bis 4 und ganz besonders bevorzugt 1 bis 3 radikalisch polymerisierbare Gruppen.The compounds (b) preferably have exactly one isocyanate-reactive group and 1 to 5, more preferably 1 to 4 and most preferably 1 to 3 radically polymerizable groups.

Bevorzugt weisen die Komponenten (b) ein Molgewicht unter 10000 g/mol auf, besonders bevorzugt unter 5000 g/mol, ganz besonders bevorzugt unter 4000 g/mol und insbesondere unter 3000 g/mol. Spezielle Verbindungen (b) weisen ein Molgewicht unter 1000 oder sogar unter 600 g/mol auf.The components (b) preferably have a molecular weight of below 10,000 g / mol, more preferably below 5000 g / mol, very preferably below 4000 g / mol and in particular below 3000 g / mol. Specific compounds (b) have a molecular weight below 1000 or even below 600 g / mol.

Gegenüber Isocyanat reaktive Gruppen können z.B. sein -OH, -SH, -NH2 und -NHR1, wobei R1 Wasserstoff oder eine 1 bis 4 Kohlenstoffatome enthaltende Alkylgruppe, wie z.B. Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sek-Butyl oder tert-Butyl, bedeutet.
Komponenten (b) können z.B. Monoester von α,β-ungesättigten Carbonsäuren, wie Acrylsäure, Methacrylsäure, Crotonsäure, Itaconsäure, Fumarsäure, Maleinsäure, Acrylamidoglykolsäure und Methacrylamidoglykolsäure sein, die vorzugsweise 2 bis 20 C-Atome und wenigstens zwei Hydroxygruppen aufweisen, wie Ethylenglykol, Diethylenglykol, Triethylenglykol, 1,2-Propylenglykol, 1,3-Propylenglykol, 1,1-Dimethyl-1,2-Ethandiol, Dipropylenglykol, Triethylenglykol, Tetraethylenglykol, Pentaethylenglykol, Tripropylenglykol, 1,2-, 1,3- oder 1,4-Butandiol, 1,5-Pentandiol, Neopentylglykol, 1,6-Hexandiol, 2-Methyl-1,5-pentandiol, 2-Ethyl-1,4-butandiol, 1,4-Dimethylolcyclohexan, 2,2-Bis(4-hydroxycyclohexyl)propan, Glycerin, Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit, Ditrimethylolpropan, Erythrit, Sorbit, Polyethylenglykol mit einer Molmasse zwischen 106 und 2000, Polypropylenglykol mit einem Molgewicht zwischen 134 und 2000, Poly-THF mit einem Molgewicht zwischen 162 und 2000 oder Poly-1,3-propandiol mit einem Molgewicht zwischen 134 und 400. Weiterhin können auch Ester oder Amide der (Meth)acrylsäure mit Aminoalkoholen z. B. 2-Aminoethanol, 2-(Methylamino)ethanol, 3-Amino-1-propa-nol, 1-Amino-2-propanol oder 2-(2-Amino-ethoxy)ethanol, 2-Mercaptoethanol oder Polyaminoalkane, wie Ethylendiamin oder Diethylentriamin, oder Vinylessigsäure verwendet werden.Isocyanate-reactive groups can be, for example, -OH, -SH, -NH 2 and -NHR 1 , where R 1 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as, for example, methyl, ethyl, n-propyl, iso -propyl, n- Butyl, iso- butyl, sec- butyl or tert- butyl, means.
Components (b) may be, for example, monoesters of α, β-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid and methacrylamidoglycolic acid, which preferably have 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, Triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,2-, 1,3- or 1,4- Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, 1,4-dimethylolcyclohexane, 2,2-bis (4- hydroxycyclohexyl) propane, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, erythritol, sorbitol, polyethylene glycol of molecular weight between 106 and 2000, polypropylene glycol of molecular weight between 134 and 2000, polyTHF of molecular weight between 162 and 2000 or poly -1,3-propanediol having a molecular weight between 134 and 400. Furthermore, esters or amides of (meth) acrylic acid with amino alcohols z. For example, 2-aminoethanol, 2- (methylamino) ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-amino-ethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine, or vinylacetic acid.

Weiterhin sind auch ungesättigte Polyether- oder Polyesterole oder Polyacrylatpolyole mit einer mittleren OH-Funktionalität von 2 bis 10 geeignet, wenn auch weniger bevorzugt.Also suitable are unsaturated polyether or polyesterols or polyacrylate polyols having an average OH functionality of 2 to 10, although less preferred.

Beispiele für Amide ethylenisch ungesättigter Carbonsäuren mit Aminoalkoholen sind Hydroxyalkyl(meth)acrylamide wie N-Hydroxymethylacrylamid, N-Hydroxymethylmethacrylamid, N-Hydroxyethylacrylamid, N-Hydroyxethylmethacrylamid, 5-Hydroxy-3-oxapentyl(meth)acrylamid, N-Hydroxyalkylcrotonamide wie N-Hydroxymethylcrotonamid oder N-Hydroxyalkylmaleinimide wie N-Hydroxyethylmaleinimid.Examples of amides of ethylenically unsaturated carboxylic acids with amino alcohols are hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxymethylmethacrylamide, 5-hydroxy-3-oxapentyl (meth) acrylamide, N-hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide or N-hydroxyalkylmaleimides such as N-hydroxyethylmaleimide.

Bevorzugt verwendet werden 2-Hydroxyethyl(meth)acrylat, 2- oder 3-Hydroxy-propyl-(meth)acrylat, 1,4-Butandiolmono(meth)acrylat, Neopentylglykolmono(meth)acrylat, 1,5-Pentandiolmono(meth)acrylat, 1,6-Hexandiolmono(meth)acrylat, Glycerinmono- und di(meth)acrylat, Trimethylolpropanmono- und di(meth)acrylat, Pentaerythritmono-, -di- und -tri(meth)acrylat sowie 2-Amino-ethyl(meth)acrylat, 2-Aminopropyl(meth)acrylat, 3-Aminopropyl(meth)acrylat, 4-Aminobutyl(meth)acrylat, 6-Aminohexyl(meth)acrylat, 2-Thioethyl(meth)acrylat, 2-Aminoethyl(meth)acrylamid, 2-Aminopropyl(meth)acrylamid, 3-Aminopropyl(meth)acryl-amid, 2-Hydroxyethyl(meth)acrylamid, 2-Hydroxypropyl(meth)acrylamid oder 3-Hydroxypropyl(meth)acrylamid. Besonders bevorzugt sind 2-Hydroxyethylacrylat, 2-Hydroxyethylmethacrylat, 2- oder 3-Hydroxypropylacrylat, 1,4-Butandiolmonoacrylat, 3-(Acryloyloxy)-2-hydroxypropyl(meth)acrylat sowie die Monoacrylate von Polyethylenglykol der Molmasse von 106 bis 238.
Es kann sich bei der Komponente (b) in einer bevorzugten Ausführungsform auch um technische Gemische der Acrylierung von Trimethylolpropan, Pentaerythrit, Ditrimethylolpropan oder Dipentaerythrit oder alkoxyliertem, bevorzugt propoxyliertem und/oder ethoxyliertem, besonders bevorzugt ethoxyliertem Trimethylolpropan, Pentaerythrit, Ditrimethylolpropan oder Dipentaerythrit handeln. Dabei handelt es sich zumeist um Gemische vollständig und unvollständig acrylierter Polyole, beispielsweise sind Verbindungen (b) technische Gemische der Acrylierung von Pentaerythrit, die zumeist eine OH-Zahl gemäß DIN 53240 von 99 bis 115 mg KOH/g aufweisen und überwiegend aus Pentaerythrittriacrylat und Pentaerythrittetraacrylat bestehen, sowie untergeordnete Mengen von Pentaerythritdiacrylat enthalten können. Dies hat den Vorteil, daß Pentaerythrittetraacrylat nicht in das erfindungsgemäße Polyurethan eingebaut wird, sondern gleichzeitig als Reaktivverdünner fungiert.Preference is given to using 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate , 1,6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate and 2-amino-ethyl (meth ) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-aminobutyl (meth) acrylate, 6-aminohexyl (meth) acrylate, 2-thioethyl (meth) acrylate, 2-aminoethyl (meth) acrylamide , 2-aminopropyl (meth) acrylamide, 3-aminopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide or 3-hydroxypropyl (meth) acrylamide. Particular preference is given to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate, 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and the monoacrylates of polyethylene glycol of molecular weight from 106 to 238.
In a preferred embodiment, component (b) may also be technical mixtures of the acrylation of trimethylolpropane, pentaerythritol, ditrimethylolpropane or dipentaerythritol or alkoxylated, preferably propoxylated and / or ethoxylated, more preferably ethoxylated trimethylolpropane, pentaerythritol, ditrimethylolpropane or dipentaerythritol. These are mostly mixtures of fully and incompletely acrylated polyols, for example, compounds (b) are technical mixtures of acrylation of pentaerythritol, which is usually a OH number according to DIN 53240 of 99 to 115 mg KOH / g and consist predominantly of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and may contain minor amounts of pentaerythritol diacrylate. This has the advantage that pentaerythritol tetraacrylate is not incorporated into the polyurethane according to the invention, but at the same time acts as a reactive diluent.

Bei der Komponente (c) handelt es sich um mindestens einen Photoinitiator mit mindestens einer gegenüber Isocyanat reaktiven Gruppe, bevorzugt mindestens einen Photoinitiator vom α-Hydroxyacetophenon-Typ oder Benzophenon-Typ, jeweils mit mindestens einer gegenüber Isocyanat reaktiven Gruppe, besonders bevorzugt mindestens einen Photoinitiator vom α-Hydroxyacetophenon-Typ.Component (c) is at least one photoinitiator having at least one isocyanate-reactive group, preferably at least one α-hydroxyacetophenone-type or benzophenone-type photoinitiator, each having at least one isocyanate-reactive group, more preferably at least one photoinitiator of α-hydroxyacetophenone type.

Als Photoinitiator wird im Rahmen dieser Schrift eine durch elektromagnetische Strahlung, bevorzugt durch UV-Strahlung, sichtbares Licht oder IR-Strahlung, besonders bevorzugt durch UV-Strahlung oder sichtbares Licht und ganz besonders bevorzugt durch UV-Strahlung in mindestens ein Radikal spaltbare Verbindung verstanden.Within the scope of this document, a photoinitiator is understood to be a compound which is capable of being cleaved by electromagnetic radiation, preferably by UV radiation, visible light or IR radiation, particularly preferably by UV radiation or visible light and very particularly preferably by UV radiation into at least one radical.

Die Komponente (c) kann eine oder mehr als eine, beispielsweise 1 bis 3, bevorzugt 1 bis 2 und besonders besonders genau eine als Photoinitiator aktive Gruppe, bevorzugt α-Hydroxyacetophenon- oder Benzophenon-Gruppe, besonders bevorzugt α-Hydroxyacetophenongruppe enthalten. Weiterhin kann die Komponente (c) eine oder mehr als eine, beispielsweise 1 bis 4, bevorzugt 1 bis 3, besonders bevorzugt 1 bis 2 und ganz besonders bevorzugt genau eine gegenüber Isocyanat reaktive Gruppe enthalten.The component (c) may contain one or more than one, for example 1 to 3, preferably 1 to 2 and particularly particularly preferably one photoinitiator active group, preferably α-hydroxyacetophenone or benzophenone group, more preferably α-hydroxyacetophenone. Furthermore, component (c) may contain one or more than one, for example 1 to 4, preferably 1 to 3, more preferably 1 to 2 and most preferably exactly one isocyanate-reactive group.

Bei den als Photoinitiator aktiven Gruppen kann es sich bevorzugt um Hydroxybenzophenone oder Hydroxyacetophenone und besonders bevorzugt um Hydroxyacetophenone handeln.The groups which are active as photoinitiator may preferably be hydroxybenzophenones or hydroxyacetophenones and more preferably hydroxyacetophenones.

Bevorzugte Komponenten (c) sind

Figure imgb0002
Figure imgb0003
 worin

  • R3, R4 und R5 jeweils unabhängig voneinander Wasserstoff, eine 1 bis 4 Kohlenstoffatome enthaltende Alkylgruppe, oder eine 1 bis 4 Kohlenstoffatome enthaltende Alkyloxygruppe,
  • p 0 (Null) oder eine ganze Zahl von 1 bis 10 sein kann und
  • Yi für i = 1 bis p unabhängig voneinander ausgewählt sein kann aus der Gruppe -CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O- und -CHPh-CH2-O-, bevorzugt aus der Gruppe -CH2-CH2-O-, -CH2-CH(CH3)-O- und -CH(CH3)-CH2-O-, und besonders bevorzugt -CH2-CH2-O-.
Preferred components (c) are
Figure imgb0002
Figure imgb0003
 wherein
  • R 3 , R 4 and R 5 are each independently hydrogen, an alkyl group containing from 1 to 4 carbon atoms, or an alkyloxy group containing from 1 to 4 carbon atoms,
  • p can be 0 (zero) or an integer from 1 to 10 and
  • Y i for i = 1 to p may independently be selected from the group -CH 2 -CH 2 -O-, -CH 2 -CH (CH 3 ) -O-, -CH (CH 3 ) -CH 2 -O -, CH 2 -C (CH 3 ) 2 -O-, -C (CH 3 ) 2 -CH 2 -O-, -CH 2 -CHVin-O-, -CHVin-CH 2 -O-, -CH 2 -CHPh-O- and -CHPh-CH 2 -O-, preferably from the group -CH 2 -CH 2 -O-, -CH 2 -CH (CH 3 ) -O- and -CH (CH 3 ) - CH 2 -O-, and more preferably -CH 2 -CH 2 -O-.

Bevorzugt befindet sich die Gruppe -O-[-Yi-]p-H in para-Stellung zur Carbonylgruppe.Preferably, the group -O - [- Y i -] p -H is in para position to the carbonyl group.

Bevorzugt sind die Reste R3, R4 und R5 unabhängig voneinander Wasserstoff oder Methyl, besonders bevorzugt Wasserstoff.The radicals R 3 , R 4 and R 5 are preferably independently of one another hydrogen or methyl, particularly preferably hydrogen.

Bevorzugt ist p 0 bis 4, besonders bevorzugt 1 bis 3 und ganz besonders bevorzugt 1.Preferably, p is 0 to 4, more preferably 1 to 3, and most preferably 1.

Bevorzugte Komponenten (c) sind 2-Hydroxy-2-methyl-1-phenyl-propan-1-on, 1-Hydroxy-cyclohexyl-phenylketon, 1-[4-[2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-on, 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-on , 2-Hydroxy-1-[4-[hydroxy-[4-(2-hydroxy-2-methyl-propanoyl)phenyl]-methyl]phenyl]-2-methyl-propan-1-on, [4-[3-(4-benzoylphenoxy)-2-hydroxy-propoxy]-phenyl]-phenyl-methanon, Benzoin, Benzoin-iso-butylether, Benzoin-tetrahydropyranylether, Benzoin-methylether, Benzoin-ethylether, Benzoin-butylether, Benzoin-iso-propylether, 7-H-Benzoin-methylether, 2-Hydroxy-2,2-dimethylacetophenon oder 1-Hyd roxyacetophenon.Preferred components (c) are 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexyl-phenylketone, 1- [4- [2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1 on, 2-hydroxy-1- [4- [hydroxy- [4- (2-hydroxy-2-methylpropanoyl) phenyl] methyl] phenyl] -2-methylpropane-1-one, [4- [ 3- (4-benzoylphenoxy) -2-hydroxy-propoxy] -phenyl] -phenyl-methanone, Benzoin, benzoin iso-butyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin iso-propyl ether, 7-H-benzoin methyl ether, 2-hydroxy-2,2-dimethyl acetophenone or 1- Hydoxyacetophenone.

Besonders bevorzugt sind 1-[4-[2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-on, 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methylpropan-1-on und 2-hydroxy-1-[4-[hydroxy-[4-(2-hydroxy-2-methyl-propanoyl)phenyl]-methyl]phenyl]-2-methyl-propan-1-on, ganz besonders bevorzugt ist 1-[4-[2-Hydroxy-ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-on.Particular preference is given to 1- [4- [2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxybenzoyl) 2-methyl-propionyl) -benzyl] -phenyl} -2-methylpropan-1-one and 2-hydroxy-1- [4- [hydroxy- [4- (2-hydroxy-2-methyl-propanoyl) -phenyl] - methyl] phenyl] -2-methyl-propan-1-one, very particular preference is given to 1- [4- [2-hydroxy-ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one ,

Bei der optionalen Komponente (d) handelt es sich um mindestens ein weiteres Di- und/oder Polyisocyanat, das von der Verbindung (a) verschieden ist. Hierbei sind auch die oben genannten Diisocyanate möglich, d.h. Verbindungen mit der Funktionalität 2.Optional component (d) is at least one other di- and / or polyisocyanate other than compound (a). In this case also the above-mentioned diisocyanates are possible, i. Connections with the functionality 2.

Als Komponente (d) kommen beispielsweise aliphatische, aromatische und cycloaliphatische Di- und Polyisocyanate mit einer NCO Funktionalität von mindestens 2, bevorzugt 2 bis 5 und besonders bevorzugt mehr als 2 bis 4 in Frage.Suitable components (d) are, for example, aliphatic, aromatic and cycloaliphatic diisocyanates and polyisocyanates having an NCO functionality of at least 2, preferably 2 to 5 and more preferably more than 2 to 4.

Als Polyisocyanate kommen Isocyanuratgruppen aufweisende Polyisocyanate, Uretdiondiisocyanate, Biuretgruppen aufweisende Polyisocyanate, Urethan- oder Allophanatgruppen aufweisende Polyisocyanate, Oxadiazintriongruppen enthaltende Polyisocyanate, Uretonimin-modifizierte Polyisocyanate von geradlinigen oder verzweigten C4-C20-Alkylendiisocyanaten, cycloaliphatischen Diisocyanaten mit insgesamt 6 bis 20 C-Atomen oder aromatischen Diisocyanaten mit insgesamt 8 bis 20 C-Atomen oder deren Gemische in Betracht. Bevorzugt sind Isocyanurate, Biurete und Allophanate, besonders bevorzugt Isocyanurate und Allophanate und ganz besonders bevorzugt Allo-phanate.Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates of straight-chain or branched C 4 -C 20 -alkylene diisocyanates, cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof. Preference is given to isocyanurates, biurets and allophanates, particularly preferably isocyanurates and allophanates and very particularly preferably allophanates.

Bei den Polyisocyanaten handelt es sich bevorzugt um Polyisocyanate auf Basis eines oder mehrerer Diisocyanate mit 4 bis 20 C-Atomen. Beispiele für übliche Diisocyanate sind aliphatische Diisocyanate wie Tetramethylendiisocyanat, Hexamethylendiisocyanat (1,6-Diisocyanatohexan), Octamethylendiisocyanat, Decamethylendiisocyanat, Dodecamethylendiisocyanat, Tetradecamethylendiisocyanat, Derivate des Lysindiisocyanates, Tetramethylxylylendiisocyanat, Trimethylhexandiisocyanat oder Tetramethylhexandiisocyanat, cycloaliphatische Diisocyanate wie 1,4-, 1,3- oder 1,2-Diisocyanatocyclohexan, 4,4'- oder 2,4'-Di(isocyanatocyclohexyl)methan, 1-Isocya-nato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexan (Isophorondiisocyanat), 1,3- oder 1,4-Bis-(isocyanatomethyl)cyclohexan oder 2,4-, oder 2,6-Diisocyanato-1-methylcyclo-hexan sowie aromatische Diisocyanate wie 2,4- oder 2,6-Toluylendiisocyanat und deren Isomerengemische, m- oder p-Xylylendiisocyanat, 2,4'- oder 4,4'-Diisocyanato-diphenylmethan und deren Isomerengemische, 1,3- oder 1,4-Phenylendiisocyanat, 1-Chlor-2,4-phenylendiisocyanat, 1,5-Naphthylendiisocyanat, Diphenylen-4,4'-diisocya-nat, 4,4'-Diisocyanato-3,3'-dimethyldiphenyl, 3-Methyldiphenylmethan-4,4'-diisocyanat, Tetramethylxylylendiisocyanat, 1,4-Diisocyanatobenzol oder Diphenylether-4,4'-diiso-cyanat.The polyisocyanates are preferably polyisocyanates based on one or more diisocyanates having 4 to 20 carbon atoms. Examples of conventional diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1.3 or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and also aromatic diisocyanates such as tolylene 2,4- or 2,6-diisocyanate and isomer mixtures thereof. or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanato-diphenylmethane and their isomer mixtures, 1,3- or 1,4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4 diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

Es können auch Gemische der genannten Diisocyanate vorliegen.There may also be mixtures of said diisocyanates.

Bevorzugt sind Hexamethylendiisocyanat, 1,3-Bis(isocyanatomethyl)cyclohexan, Isophorondiisocyanat und Di(isocyanatocyclohexyl)methan, besonders bevorzugt ist Hexamethylendiisocyanat.Preference is given to hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane, particularly preferably hexamethylene diisocyanate.

Die einsetzbaren Polyisocyanate haben bevorzugt einen Gehalt an Isocyanatgruppen (berechnet als NCO, Molekulargewicht = 42) von 10 bis 60 Gew% bezogen auf das Di- und Polyisocyanat(gemisch), bevorzugt 15 bis 60 Gew% und besonders bevorzugt 20 bis 55 Gew%.The usable polyisocyanates preferably have a content of isocyanate groups (calculated as NCO, molecular weight = 42) of 10 to 60% by weight, based on the diisocyanate and polyisocyanate (mixture), preferably 15 to 60% by weight and particularly preferably 20 to 55% by weight.

Bevorzugt sind die Polyisocyanate aufgebaut aus aliphatischen und/oder cycloaliphatischen Polyisocyanaten, z.B. die vorstehend genannten aliphatischen bzw. cycloaliphatischen Diisocyanate, oder deren Mischungen.Preferably, the polyisocyanates are composed of aliphatic and / or cycloaliphatic polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

Als Komponente (e) kommen Verbindungen in Betracht, die mindestens zwei gegenüber Isocyanat reaktive Gruppen, beispielsweise -OH, -SH, -NH2 oder -NHR2, worin R2 darin unabhängig voneinander Wasserstoff, Methyl, Ethyl, iso-Propyl, n-Propyl, n-Butyl, iso-Butyl, sek-Butyl oder tert-Butyl bedeuten kann, aufweisen.Suitable components (e) are compounds containing at least two isocyanate-reactive groups, for example -OH, -SH, -NH 2 or -NHR 2 , in which R 2 independently of one another is hydrogen, methyl, ethyl, isopropyl , n Propyl, n-butyl, iso -butyl, sec- butyl or tert -butyl.

Verbindungen (e) mit genau 2 gegenüber Isocyanat reaktiven Gruppen sind bevorzugt 2 bis 20 Kohlenstoffatome aufweisende Diole, z.B. Ethylenglykol, 1,2-Propandiol, 1,3-Propandiol, 1,1-Dimethylethan-1,2-diol, 2-Butyl-2-ethyl-1,3-Propandiol, 2-Ethyl-1,3-Propandiol, 2-Methyl-1,3-Propandiol, Neopentylglykol, Hydroxypivalinsäureneopentylglykolester, 1,2-, 1,3- oder 1,4-Butandiol, 1,6-Hexandiol, 1,10-Dekandiol, Bis-(4-hydroxycyclohexan)isopropyliden, Tetramethylcyclobutandiol, 1,2-, 1,3- oder 1,4-Cyclohexandiol, Cyclooctandiol, Norbornandiol, Pinandiol, Decalindiol, 2-Ethyl-1,3-Hexandiol, 2,4-Diethyl-oktan-1,3-diol, Hydrochinon, Bisphenol A, Bisphenol F, Bisphenol B, Bisphenol S, 2,2-Bis(4-hydroxycyclohexyl)propan, 1,1-, 1,2-, 1,3- und 1,4-Cyclohexandimethanol, 1,2-, 1,3- oder 1,4-Cyclohexandiol, Poly-THF mit einer Molmasse zwischen 162 und 2000, Poly-1,2-propandiol oder Poly-1,3-propandiol mit einer Molmasse zwischen 134 und 1178 oder Polyethylenglykol mit einer Molmasse zwischen 106 und 2000 sowie aliphatische Diamine, wie Methylen-, und Isopropyliden-bis-(cyclohexylamin), Piperazin, 1,2-, 1,3- oder 1,4-Diaminocyclohexan, 1,2-, 1,3- oder 1,4-Cyclohexan-bis-(methylamin), etc., Dithiole oder mehrfunktionelle Alkohole, sekundäre oder primäre Aminoalkohole, wie Ethanolamin, Monopropanolamin etc. oder Thioalkohole, wie Thioethylenglykol.Compounds (e) having exactly 2 isocyanate-reactive groups are preferably diols having 2 to 20 carbon atoms, for example ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol, 2-butyl 2-ethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 1,2-, 1,3- or 1,4-butanediol , 1,6-hexanediol, 1,10-decanediol, bis (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalindiol, 2- Ethyl 1,3-hexanediol, 2,4-diethyl-octane-1,3-diol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, 1,2-, 1,3- or 1,4-cyclohexanediol, poly-THF with a molecular weight between 162 and 2000, poly-1, 2-propanediol or poly-1,3-propanediol having a molecular weight between 134 and 1178 or polyethylene glycol having a molecular weight between 106 and 200 0 and aliphatic diamines, such as methylene, and isopropylidene-bis (cyclohexylamine), piperazine, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4- Cyclohexane bis (methylamine), etc., dithiols or polyfunctional alcohols, secondary or primary amino alcohols such as ethanolamine, monopropanolamine, etc., or thioalcohols such as thioethylene glycol.

Besonders geeignet sind hier die cycloaliphatischen Diole, wie z.B. Bis-(4-hydroxycyclohexan) isopropyliden, Tetramethylcyclobutandiol, 1,2-, 1,3- oder 1,4-Cyclohexandiol, 1,1-, 1,2-, 1,3- und 1,4-Cyclohexandimethanol, Cyclooctandiol oder Norbornandiol.Particularly suitable here are the cycloaliphatic diols, e.g. Bis (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, cyclooctanediol or norbornanediol.

Weitere Verbindungen (e) können Verbindungen mit mindestens drei gegenüber Isocyanat reaktiven Gruppen sein.Other compounds (e) may be compounds having at least three isocyanate-reactive groups.

Beispielsweise können diese Komponenten 3 bis 6, bevorzugt 3 bis 5, besonders bevorzugt 3 bis 4 und ganz besonders bevorzugt 3 gegenüber Isocyanat reaktiven Gruppen aufweisen.For example, these components may have 3 to 6, preferably 3 to 5, more preferably 3 to 4 and most preferably 3 isocyanate-reactive groups.

Das Molekulargewicht dieser Komponenten beträgt in der Regel nicht mehr als 2000 g/mol, bevorzugt nicht mehr als 1500 g/mol, besonders bevorzugt nicht mehr als 1000 g/mol und ganz besonders bevorzugt nicht mehr als 500 g/mol.The molecular weight of these components is generally not more than 2000 g / mol, preferably not more than 1500 g / mol, more preferably not more than 1000 g / mol and most preferably not more than 500 g / mol.

Dies sind bevorzugt 2 bis 20 Kohlenstoffatome aufweisende Polyole, beispielsweise Trimethylolbutan, Trimethylolpropan, Trimethylolethan, Pentaerythrit, Glycerin, Ditrimethylolpropan, Dipentaerythrit, Sorbit, Mannit, Diglycerol, Threit, Erythrit, Adonit (Ribit), Arabit (Lyxit), Xylit, Dulcit (Galactit), Maltit, Isomalt, besonders bevorzugt sind Trimethylolpropan, Pentaerythrit und Glycerin und ganz besonders bevorzugt Trimethylolpropan.These are preferably 2 to 20 carbon atoms, for example trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol) ), Maltitol, isomalt, particularly preferred are trimethylolpropane, pentaerythritol and glycerol, and most preferably trimethylolpropane.

Optionale Komponenten (f) sind solche mit gegebenenfalls mindestens einer Verbindung mit genau einer gegenüber Isocyanat reaktiven Gruppe. In einer bevorzugten Ausführungsform ist mindestens eine Komponente (f) anwesend.Optional components (f) are those with optionally at least one compound having exactly one isocyanate-reactive group. In a preferred embodiment, at least one component (f) is present.

Dabei handelt es sich bevorzugt um Monoole, besonders bevorzugt um Alkanole und ganz besonders bevorzugt um Alkanole mit 1 bis 20, bevorzugt 1 bis 12, besonders bevorzugt 1 bis 6, ganz besonders bevorzugt 1 bis 4 und insbesondere 1 bis 2 Kohlenstoffatome.These are preferably monools, particularly preferably alkanols and very particularly preferably alkanols having 1 to 20, preferably 1 to 12, particularly preferably 1 to 6, very particularly preferably 1 to 4 and in particular 1 to 2 carbon atoms.

Beispiele dafür sind Methanol, Ethanol, iso-Propanol, n-Propanol, n-Butanol, iso-Butanol, sek-Butanol, tert-Butanol, n-Hexanol, n-Heptanol, n-Octanol, n-Decanol, iso Decanol-Isomerengemische, Undecanol, n-Dodecanol (Laurylalkohol), iso Tridecanol-Isomerengemische, n Tridecanol, Tetradecanol, Pentadecanol, Hexadecanol, Heptadecanol, Octadecanol, Nonadecanol, Eicosanol, 2-Ethylhexanol, Cyclopentanol, Cyclohexanol, Cyclooctanol, Cyclododecanol, Ethylenglykolmonomethylether, Ethylenglykolmonoethylether, Diethylenglykol, 1,3-Propandiolmonomethylether, bevorzugt sind Methanol, Ethanol, iso-Propanol, n-Propanol, n-Butanol, tert-Butanol, n-Hexanol, 2-Ethylhexanol, Cyclopentanol, Cyclohexanol, und Cyclododecanol, besonders bevorzugt sind Methanol, Ethanol, iso-Propanol, n-Propanol, n-Butanol und tert-Butanol, ganz besonders bevorzugt sind n-Propanol, und Ethanol und insbesondere Ethanol.Examples thereof are methanol, ethanol, isopropanol , n-propanol, n-butanol, isobutanol , sec- butanol, tert- butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, iso- decanol- Isomer mixtures, undecanol, n-dodecanol (lauryl alcohol), iso tridecanol isomer mixtures, n tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, 2-ethylhexanol, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol , 1,3-Propandiolmonomethylether, preferred are methanol, ethanol, iso -propanol, n-propanol, n-butanol, tert -butanol, n-hexanol, 2-ethylhexanol, cyclopentanol, cyclohexanol, and cyclododecanol, particularly preferred are methanol, ethanol , iso -propanol, n-propanol, n-butanol and tert- butanol, very particularly preferred are n-propanol, and ethanol and especially ethanol.

In einer weniger bevorzugten, aber möglichen Ausführungsform kann es sich bei den Monoolen um die genannten cycloaliphatischen Alkohole handeln, bevorzugt um Cyclopentanol oder Cyclohexanol, besonders bevorzugt um Cyclohexanol.In a less preferred but possible embodiment, the monools may be the said cycloaliphatic alcohols, preferably cyclopentanol or cyclohexanol, more preferably cyclohexanol.

In einer weiteren bevorzugten Ausführungsform kann es sich bei den Monoolen um die genannten aliphatischen Alkohole mit 6 bis 20 Kohlenstoffatomen handeln, besonders bevorzugt um solche mit 8 bis 20 Kohlenstoffatomen, ganz besonders bevorzugt um solche mit 10 bis 20 Kohlenstoffatomen.In a further preferred embodiment, the monools can be the stated aliphatic alcohols having 6 to 20 carbon atoms, more preferably those having 8 to 20 carbon atoms, very particularly preferably those having 10 to 20 carbon atoms.

In einer besonders bevorzugten Ausführungsform handelt es sich bei den Monoolen um die genannten aliphatischen Alkohole handeln, ganz besonders bevorzugt um die mit 1 bis 4 Kohlenstoffatomen, insbesondere Ethanol.In a particularly preferred embodiment, the monools are the aliphatic alcohols mentioned, very particularly preferably those having 1 to 4 carbon atoms, in particular ethanol.

In einer alternativen weiteren besonders bevorzugt Ausführungsform handelt es sich bei den Monoolen um alkoxylierte aliphatischen Alkohole der Formel

        R9-O-[-Zi-]q-H

handeln, worin

  • R9 einen 1 bis 20 Kohlenstoffatome, bevorzugt 10 bis 20 Kohlenstoffatome aufweisenen Alkylrest,
  • q eine positive ganze Zahl von 1 bis 15, bevorzugt 1 bis 10 und
  • Zi für i = 1 bis q unabhängig voneinander ausgewählt sein kann aus der Gruppe -CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O- und -CHPh-CH2-O-, bevorzugt aus der Gruppe -CH2-CH2-O-, -CH2-CH(CH3)-O- und -CH(CH3)-CH2-O-, und besonders bevorzugt -CH2-CH2-O-
bedeuten.In an alternative further particularly preferred embodiment, the monools are alkoxylated aliphatic alcohols of the formula

R 9 -O - [- Z i -] q -H

act in which
  • R 9 is an alkyl radical having 1 to 20 carbon atoms, preferably 10 to 20 carbon atoms,
  • q is a positive integer of 1 to 15, preferably 1 to 10 and
  • Z i for i = 1 to q can be independently selected from the group -CH 2 -CH 2 -O-, -CH 2 -CH (CH 3 ) -O-, -CH (CH 3 ) -CH 2 -O -, CH 2 -C (CH 3 ) 2 -O-, -C (CH 3 ) 2 -CH 2 -O-, -CH 2 -CHVin-O-, -CHVin-CH 2 -O-, -CH 2 -CHPh-O- and -CHPh-CH 2 -O-, preferably from the group -CH 2 -CH 2 -O-, -CH 2 -CH (CH 3 ) -O- and -CH (CH 3 ) - CH 2 -O-, and more preferably -CH 2 -CH 2 -O-
mean.

Bei Einsatz derartiger alkoxylierter aliphatischer Alkohole als Komponente (f) in den erfindungsgemäßen Polyurethanen (A) zeigen die so erhältlichen Polyurethane (A) zusätzlich zu ihren sonstigen positiven Eigenschaften eine verbesserte Dispergierung von Pigmenten in den erfindungsgemäßen Tinten und Druckfarben, was im Druck eine erhöhte Farbdichte ermöglicht.When using such alkoxylated aliphatic alcohols as component (f) in the polyurethanes (A) according to the invention, the polyurethanes (A) thus obtainable show, in addition to their other positive properties, an improved dispersion of pigments in the inks and printing inks according to the invention, resulting in an increased color density in the printing process allows.

Die erfindungsgemäß verwendbaren Polyurethane werden durch Reaktion der Komponenten (a), (b) und (c) sowie gegebenenfalls (d) und/oder (e) und/oder (f) miteinander erhalten.The polyurethanes which can be used according to the invention are obtained by reacting the components (a), (b) and (c) and optionally (d) and / or (e) and / or (f) with one another.

Dabei ist die molare Zusammensetzung (a):(b):(c):(d):(e):(f) pro 1 mol reaktive Isocycanatgruppen in (a) und (d) zusammen in der Regel wie folgt:

  • (b) 1 - 50, bevorzugt 5 - 40, besonders bevorzugt 10 - 37,5 und insbesondere 15 - 33 mol% an gegenüber Isocyanat reaktive Gruppen,
  • (c) 1 - 50, bevorzugt 5 - 40, besonders bevorzugt 10 - 37,5 und insbesondere 15 - 33 mol% an gegenüber Isocyanat reaktive Gruppen,
  • (e) 0 - 50, bevorzugt 0 - 30, besonders bevorzugt 0 - 25 und insbesondere 0 - 20 und speziell 0 mol% an gegenüber Isocyanat reaktiven Gruppen,
  • (f) 0 - 5, bevorzugt 0,1 - 3 und besonders bevorzugt 0,2 - 2 mol% an gegenüber Isocyanat reaktiven Gruppen,
mit der Maßgabe, daß die Summe der gegenüber Isocyanat reaktiven Gruppen der Anzahl der Isocyanatgruppen in (a) und (d) entspricht, soweit diese nicht unter Bildung von oligomeren Polyisocyanaten mit anderen Isocyanatgruppen, beispielsweise unter Bildung von Dimeren oder Trimeren, abregiert sind. Der Anteil an Isocyanatgruppen aus (d) an der Summe der Isocyanatgruppen in (a) und (d) kann beispielsweise bis zu 50% betragen, bevorzugt bis zu 25%, besonders bevorzugt bis zu 10% und ganz besonders bevorzugt 0, d.h. es ist keine Verbindung (d) anwesend.The molar composition (a) :( b) :( c) :( d) :( e) :( f) per 1 mol of reactive isocycanate groups in (a) and (d) together is generally as follows:
  • (b) 1-50, preferably 5-40, particularly preferably 10-37.5 and in particular 15-33 mol% of isocyanate-reactive groups,
  • (c) 1-50, preferably 5-40, more preferably 10-37.5 and in particular 15-33 mol% of isocyanate-reactive groups,
  • (e) 0-50, preferably 0-30, particularly preferably 0-25 and in particular 0-20 and especially 0 mol% of isocyanate-reactive groups,
  • (f) 0-5, preferably 0.1-3 and particularly preferably 0.2-2 mol% of isocyanate-reactive groups,
with the proviso that the sum of the isocyanate-reactive groups corresponds to the number of isocyanate groups in (a) and (d), provided that they are not abregiert to form oligomeric polyisocyanates with other isocyanate groups, for example, to form dimers or trimers. The proportion of isocyanate groups from (d) on the sum of the isocyanate groups in (a) and (d) can be, for example, up to 50%, preferably up to 25%, particularly preferably up to 10% and very particularly preferably 0, ie no compound (d) present.

In der bevorzugten Ausführungsform, in der ein allophanatgruppenhaltiges Polyisocyanat der Formel (I), bei dem es sich bereits um ein Addukt der Komponenten (a) und (b) handelt, zur Herstellung des erfindungsgemäßen Polyurethans (A) eingesetzt wird, ist die molare Zusammensetzung pro reaktive Isocycanatgruppen in der Verbindung der Formel (I) wie folgt:

  • (b) 0 bis 30 mol%, bevorzugt 0 bis 20, besonders bevorzugt 0 bis 10 und ganz besonders bevorzugt 0 mol% an gegenüber Isocyanat reaktive Gruppen,
  • (c) 50 bis 100 mol%, bevorzugt 60 bis 90 und besonders bevorzugt 60 bis 80 mol% an gegenüber Isocyanat reaktive Gruppen,
  • (d) 0 bis 30 mol%, bevorzugt 0 bis 20, besonders bevorzugt 0 bis 10 und ganz besonders bevorzugt 0 mol% Isocyanatgruppen,
  • (e) 0 bis 20 mol%, bevorzugt 0 bis 10, besonders bevorzugt 0 bis 50 und ganz besonders bevorzugt 0 mol% an gegenüber Isocyanat reaktive Gruppen,
  • (f) 0 - 20, bevorzugt 0,1 - 20 und besonders bevorzugt 0,2 - 20 mol% an gegenüber Isocyanat reaktiven Gruppen,
mit der Maßgabe, daß die Summe an gegenüber Isocyanat reaktiven Gruppen der Summe an Isocyanatgruppen entspricht.In the preferred embodiment in which an allophanate group-containing polyisocyanate of the formula (I), which is already an adduct of components (a) and (b), is used to prepare the polyurethane (A) according to the invention, the molar composition is per reactive isocyanate groups in the compound of formula (I) as follows:
  • (b) 0 to 30 mol%, preferably 0 to 20, particularly preferably 0 to 10 and very particularly preferably 0 mol% of isocyanate-reactive groups,
  • (c) 50 to 100 mol%, preferably 60 to 90 and particularly preferably 60 to 80 mol% of isocyanate-reactive groups,
  • (d) 0 to 30 mol%, preferably 0 to 20, particularly preferably 0 to 10 and very particularly preferably 0 mol% of isocyanate groups,
  • (e) 0 to 20 mol%, preferably 0 to 10, particularly preferably 0 to 50 and very particularly preferably 0 mol% of isocyanate-reactive groups,
  • (f) 0-20, preferably 0.1-20 and more preferably 0.2-20 mol% of isocyanate-reactive groups,
with the proviso that the sum of isocyanate-reactive groups corresponds to the sum of isocyanate groups.

Die Bildung des Addukts aus isocyanatgruppenhaltiger Verbindung und der Verbindung, die gegenüber Isocyanatgruppen reaktive Gruppen enthält erfolgt in der Regel durch Mischen der Komponenten in beliebiger Reihenfolge, gegebenenfalls bei erhöhter Temperatur.The formation of the adduct of isocyanate group-containing compound and the compound containing isocyanate-reactive groups is generally carried out by mixing the components in any order, optionally at elevated temperature.

Bevorzugt wird dabei die Verbindung, die gegenüber Isocyanatgruppen reaktive Gruppen enthält, zu der isocyanatgruppenhaltigen Verbindung zugegeben, bevorzugt in mehreren Schritten.In this case, the compound containing isocyanate-reactive groups is preferably added to the compound containing isocyanate groups, preferably in several steps.

Besonders bevorzugt wird die isocyanatgruppenhaltige Verbindung (a) sowie gegebenenfalls (d) vorgelegt und die Verbindungen, die gegenüber Isocyanat reaktive Gruppen enthalten, zugegeben. Insbesondere wird die isocyanatgruppenhaltige Verbindung (a) vorgelegt und daraufhin (b) und/oder (c), bevorzugt (b) zugegeben. Nachfolgend können gegebenenfalls gewünschte weitere Komponenten zugegeben werden.Particular preference is given to the isocyanate group-containing compound (a) and optionally (d) and the compounds containing isocyanate-reactive groups added. In particular, the isocyanate group-containing compound (a) is initially charged and then (b) and / or (c), preferably (b), are added. Subsequently, optionally desired further components can be added.

In der Regel wird die Reaktion bei Temperaturen zwischen 5 und 100 °C, bevorzugt zwischen 20 bis 90 °C und besonders bevorzugt zwischen 40 und 80°C und insbesondere zwischen 60 und 80 °C durchgeführt.In general, the reaction is carried out at temperatures between 5 and 100 ° C, preferably between 20 to 90 ° C and more preferably between 40 and 80 ° C and in particular between 60 and 80 ° C.

Das erfindungsgemäße Verfahren wird durchgeführt in Gegenwart von weniger als 1000 Gew.ppm, bevorzugt weniger als 500, besonders bevorzugt weniger als 250 und ganz besonders bevorzugt weniger als 100 Gew.ppm einer Wismut-, Zink- und/oder Titan-haltigen Verbindung, bevorzugt einer Wismut- und/oder Titan-haltigen Verbindung und besonders bevorzugt einer Wismut-haltigen Verbindung.The process according to the invention is carried out in the presence of less than 1000 ppm by weight, preferably less than 500, more preferably less than 250 and very preferably less than 100 ppm by weight of a bismuth, zinc and / or titanium-containing compound a bismuth and / or titanium-containing compound, and more preferably a bismuth-containing compound.

Als Zink- und Wismutverbindungen kommen dabei solche in Betracht, in denen folgende Anionen eingesetzt werden: F-, Cl-, ClO-, ClO3 -, ClO4 -, Br-, J-, JO3 -, CN-, OCN-, NO2 -, NO3 -, HCO3 -, CO3 2-, S2-, SH-, HSO3 -, SO3 2-, HSO4 -, SO4 2-, S2O2 2-, S2O4 2-, S2O5 2-, S2O6 2-, S2O7 2-, S2O8 2-, H2PO2 -, H2PO4 -, HPO4 2-, PO4 3-, P2O7 4-, (OCnH2n-1)-, (CnH2n-1O2)-, (CnH2n-3O2)- sowie (Cn+1H2n-2O4)2-, wobei n für die Zahlen 1 bis 20 steht. Bevorzugt sind dabei die Carboxylate, bei denen das Anion den Formeln (CnH2n-1O2)- sowie (Cn+1H2n-2O4)2- mit n gleich 1 bis 20, gehorcht. Besonders bevorzugte Salze weisen als Anionen Monocarboxylate der allgemeinen Formel (CnH2n-1O2)- auf, wobei n für die Zahlen 1 bis 20 steht. Hierbei sind insbesondere zu erwähnen Format, Acetat, Propionat, Hexanoat, Neodekanoat und 2-Ethylhexanoat.When zinc and bismuth compounds is given to those eligible, in which the following anions are used: F -, Cl -, ClO -, ClO 3 -, ClO 4 -, Br -, J -, JO 3 -, CN -, OCN - , NO 2 -, NO 3 -, HCO 3 -, CO 3 2-, S 2-, SH -, HSO 3 -, SO 3 2-, HSO 4 -, SO 4 2-, S 2 O 2 2-, S 2 O 4 2-, S 2 O 5 2-, S 2 O 6 2-, S 2 O 7 2-, S 2 O 8 2-, H 2 PO 2 -, H 2 PO 4 -, HPO 4 2 - , PO 4 3- , P 2 O 7 4- , (OC n H 2n-1 ) - , (C n H 2n-1 O 2 ) - , (C n H 2n-3 O 2 ) - as well as (C n + 1 H 2n-2 O 4 ) 2- , where n is the numbers 1 to 20. Preferred are the carboxylates in which the anion conforms to the formulas (C n H 2n-1 O 2 ) - as well as (C n + 1 H 2n-2 O 4 ) 2- with n equal to 1 to 20. Particularly preferred salts have as anions monocarboxylates of the general formula (C n H 2n-1 O 2 ) - , where n is the numbers 1 to 20. Particular mention should be made here of format, acetate, propionate, hexanoate, neodecanoate and 2-ethylhexanoate.

Unter den Zink-Katalysatoren sind die Zink-carboxylate bevorzugt, besonders bevorzugt solche von Carboxylaten, die mindestens sechs Kohlenstoffatome, ganz besonders bevorzugt mindestens acht Kohlenstoffatome aufweisen, insbesondere Zink-(II)-diacetat oder Zink-(II)-dioctoat oder Zink-(II) neodecanoat. Handelsübliche Katalysatoren sind beispielsweise Borchi® Kat 22 von OMG Borchers GmbH, Langenfeld, Deutschland.Among the zinc catalysts, the preferred zinc carboxylates are those of carboxylates which have at least six carbon atoms, very particularly preferably at least eight carbon atoms, in particular zinc (II) diacetate or zinc (II) dioctoate or zinc carbonate. (II) neodecanoate. Commercially available catalysts are, for example, Borchi® Kat 22 from OMG Borchers GmbH, Langenfeld, Germany.

Unter den Wismut-Katalysatoren sind die Wismut-carboxylate bevorzugt, besonders bevorzugt solche von Carboxylaten, die mindestens sechs Kohlenstoffatome aufweisen, insbesondere Wismut-octoate, -ethylhexanoate, -neodecanoate, oder -pivalate; beispielsweise K-KAT 348, XC-B221; XC-C227, XC 8203 und XK-601 von King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 von TIB Chemicals und solchen von Shepherd Lausanne, sowie beispielsweise Borchi® Kat 24; 315; 320 von OMG Borchers GmbH, Langenfeld, Deutschland.Among the bismuth catalysts, the bismuth carboxylates are preferred, more preferably those of carboxylates having at least six carbon atoms, especially bismuth octoates, ethyl hexanoates, neodecanoates, or pivalates; for example, K-KAT 348, XC-B221; XC-C227, XC 8203 and XK-601 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals and those from Shepherd Lausanne, and, for example, Borchi® Kat 24; 315; 320 from OMG Borchers GmbH, Langenfeld, Germany.

Es kann sich dabei auch um Gemische verschiedener Metalle handeln, wie beispielsweise in Borchi® Kat 0245 von OMG Borchers GmbH, Langenfeld, DeutschlandThese may also be mixtures of different metals, as for example in Borchi® Kat 0245 from OMG Borchers GmbH, Langenfeld, Germany

Unter den Titanverbindungen sind die Titan tetra-alkoholate Ti(OR)4 bevorzugt, besonders bevorzugt solche von Alkoholen ROH mit 1 bis 8 Kohlenstoffatomen, beispielsweise Methanol, Ethanol, iso-Propanol, n-Propanol, n-Butanol, iso-Butanol, sek-Butanol, tert-Butanol, n-Hexanol, n-Heptanol, n-Octanol, bevorzugt sind Methanol, Ethanol, iso-Propanol, n-Propanol, n-Butanol, tert-Butanol, besonders bevorzugt sind iso-Propanol und n-Butanol.Among the titanium compounds, the titanium tetra-alcoholates Ti (OR) 4 are preferred, more preferably those of alcohols ROH having 1 to 8 carbon atoms, for example, methanol, ethanol, iso -propanol, n-propanol, n-butanol, iso -butanol, sec Butanol, tert- butanol, n-hexanol, n-heptanol, n-octanol, are preferably methanol, ethanol, iso -propanol, n-propanol, n-butanol, tert -butanol, particularly preferably isopropanol and n- butanol.

Im erfindungsgemäßen Verfahren wird dabei unter wasserfreien Bedingungen gearbeitet.
Wasserfrei bedeutet dabei, daß der Wassergehalt im Reaktionssystem nicht mehr als 5 Gew% beträgt, bevorzugt nicht mehr als 3 Gew% und besonders bevorzugt nicht mehr als 1 Gew%, ganz besonders bevorzugt nicht mehr als 0,75 und insbesondere nicht mehr als 0,5 Gew%. Wird nicht wasserfrei gearbeitet besteht die Gefahr, daß unter den Reaktionsbedingungen Wasser mit den freien Isocyanatgruppen reagiert und die sich bildenden Aminogruppen Nebenreaktion verursachen, beispielsweise eine Michael-Addition an (Meth)acrylatgruppen oder mit weiteren freien Isocyanatgruppen zu schwer löslichen Biureten reagieren.In the process according to the invention is carried out under anhydrous conditions.
Anhydrous here means that the water content in the reaction system is not more than 5% by weight, preferably not more than 3% by weight and particularly preferably not more than 1% by weight, very particularly preferably not more than 0.75 and in particular not more than 0, 5% by weight. If not worked anhydrous there is a risk that under the reaction conditions water reacts with the free isocyanate groups and cause the forming amino groups side reaction, for example, a Michael addition to (meth) acrylate or react with other free isocyanate groups to poorly soluble biurets.

Bevorzugt wird die Reaktion in Gegenwart mindestens eines sauerstoffhaltigen Gases durchgeführt, z.B. Luft oder Luft-Stickstoff-Gemische oder Gemische aus Sauerstoff oder einem sauerstoffhaltigen Gas mit einem unter den Reaktionsbedingungen inerten Gas, die einen Sauerstoffgehalt unter 15, bevorzugt unter 12, besonders bevorzugt unter 10, ganz besonders bevorzugt unter 8 und insbesondere unter 6 Vol% aufweisen.Preferably, the reaction is carried out in the presence of at least one oxygen-containing gas, e.g. Air or air-nitrogen mixtures or mixtures of oxygen or an oxygen-containing gas with an inert gas under the reaction conditions, which have an oxygen content of less than 15, preferably less than 12, more preferably less than 10, most preferably less than 8 and in particular less than 6 vol% ,

In einer bevorzugten Ausführungsform wird dem Reaktionsgemisch bis zu
1000 Gew.ppm mindestens eines Prozeßstabilisators zugegeben. Bevorzugte Prozeßstabilisatoren sind Phenothiazin, 2,2,6,6-Tetramethylpiperidin-N-oxyl sowie Chinonmethide.In a preferred embodiment, the reaction mixture is up to
1000 Gew.ppm added to at least one process stabilizer. Preferred process stabilizers are phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl and quinone methides.

In einer bevorzugten Ausführungsform wird die Umsetzung der isocyanatgruppenhaltigen Verbindung (a) oder des Reaktionsproduktes aus (a) und (b) mit der Verbindung (c) so durchgeführt, daß man die isocyanatgruppenhaltige Verbindung in einem Überschuß an NCO-Gruppen bezogen auf die gegenüber Isocyanat reaktiven Gruppen in (c) von mindestens 20 mol% einsetzt. Dies hat zur Folge, daß die Verbindungen (c) im wesentlichen vollständig einreagieren. Der Überschuß an Isocyanatgruppen kann anschließend mit weiterer Verbindung (b) und/oder Verbindung (f), bevorzugt mit Verbindung (f) umgesetzt werden.In a preferred embodiment, the reaction of the isocyanate group-containing compound (a) or the reaction product of (a) and (b) with the compound (C) carried out by using the isocyanate group-containing compound in an excess of NCO groups based on the isocyanate-reactive groups in (c) of at least 20 mol%. This has the consequence that the compounds (c) react substantially completely. The excess of isocyanate groups can then be reacted with further compound (b) and / or compound (f), preferably with compound (f).

Die Reaktion kann auch in Gegenwart eines inerten Solvens durchgeführt werden, z.B. Aceton, Iso-butyl-methylketon, Toluol, Xylol, Butylacetat, Methoxypropylacetat oder Ethoxyethylacetat. Bevorzugt wird die Reaktion jedoch in Abwesenheit eines Solvens durchgeführt.The reaction may also be carried out in the presence of an inert solvent, such as acetone, iso-butyl-methyl ketone, toluene, xylene, butyl acetate, methoxypropyl acetate or ethoxyethyl acetate. Preferably, however, the reaction is carried out in the absence of a solvent.

In einer bevorzugten Ausführungsform wird die Umsetzung von (a) mit (b) und/oder (c), bevorzugt (a) und (b) unter Allophanatisierungsbedingungen durchgeführt. Darunter werden Reaktionsbedingungen verstanden, unter denen zumindest teilweise Allophanatgruppen gebildet werden, bevorzugt solche Reaktionsbedingungen, unter denen von verschiedenen konkurrierenden Reaktionen der Isocyanatgruppen mehr isocyanatgruppen zu Allophanatgruppen abreagieren als zu anderen Reaktionsprodukten.In a preferred embodiment, the reaction of (a) with (b) and / or (c), preferably (a) and (b) is carried out under allophanatization conditions. These are to be understood as meaning reaction conditions under which allophanate groups are formed at least in part, preferably those reaction conditions under which more isocyanate groups of various competing reactions of the isocyanate groups react to form allophanate groups than to other reaction products.

In einer weiteren bevorzugten Ausführungsform werden solche Verbindungen eingesetzt, wie in der WO 00/39183 , S.4, Z. 3 bis S. 10, Z. 19 beschrieben, deren Offenbarung hiermit Bestandteil der vorliegenden Schrift sei. Besonders bevorzugt sind unter diesen solche Verbindungen, die als Aufbaukomponenten mindestens ein Allophanatgruppen aufweisendes, (cyclo)aliphatisches Isocyanat und mindestens ein Hydroxyalkyl(meth)acrylat aufweisen, ganz besonders bevorzugt die Produkt Nr. 1 bis 9 in Tabelle 1 auf S. 24 der WO 00/39183 . Ganz besonders bevorzugt handelt es sich dabei um solche Polyisocyanate der oben beschriebenen Formel (I).In a further preferred embodiment, such compounds are used as in the WO 00/39183 , P.4, Z. 3 to p. 10, Z. 19, the disclosure of which is herewith part of the present document. Particularly preferred among these are those compounds which have as structural components at least one (cyclo) aliphatic isocyanate containing allophanate groups and at least one hydroxyalkyl (meth) acrylate, very particularly preferably the product Nos. 1 to 9 in Table 1 on page 24 of the WO 00/39183 , Very particular preference is given to those polyisocyanates of the formula (I) described above.

Die vorliegende Beschreibung beschreibt ferner Formulierungen von einbaubaren Photoinitiatoren, bestehend aus
mindestens einem Polyurethan A, enthaltend als Aufbaukomponenten

  1. (a) mindestens ein organisches aliphatisches, aromatisches oder cycloaliphatisches Di- oder Polyisocyanat mit einer Funktionalität von mehr als 2,
  2. (b) mindestens eine Verbindung mit jeweils mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren ungesättigten Gruppe,
  3. (c) mindestens einen Photoinitiator mit mindestens einer gegenüber Isocyanat reaktiven Gruppe,
  4. (d) gegebenenfalls mindestens ein weiteres Di- und/oder Polyisocyanat, das von der Verbindung (a) verschieden ist,
  5. (e) gegebenenfalls mindestens eine Verbindung mit mindestens zwei gegenüber Isocyanat reaktiven Gruppen,
  6. (f) gegebenenfalls mindestens eine Verbindung mit genau einer gegenüber Isocyanat reaktiven Gruppe, optional mindestens eine multifunktionelle polymerisationsfähige Verbindung (B)
sowie 0,5 bis 4 Gew% Wasser, bezogen auf die Menge Polyurethan (A).The present specification further describes formulations of incorporable photoinitiators consisting of
at least one polyurethane A, containing as structural components
  1. (a) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate having a functionality of more than 2,
  2. (b) at least one compound having in each case at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group,
  3. (c) at least one photoinitiator having at least one isocyanate-reactive group,
  4. (d) optionally, at least one further di- and / or polyisocyanate other than compound (a),
  5. (e) optionally, at least one compound having at least two isocyanate-reactive groups,
  6. (f) optionally at least one compound having exactly one isocyanate-reactive group, optionally at least one multifunctional polymerizable compound (B)
and 0.5 to 4% by weight of water, based on the amount of polyurethane (A).

Der Gehalt an Wasser beträgt bevorzugt mindestens 0,75 Gew%, besonders bevorzugt mindestens 1 Gew%, ganz besonders bevorzugt mindestens 1,25 Gew% und insbesondere mindestens 1,5 Gew%, bezogen auf die Menge Polyurethan (A).The content of water is preferably at least 0.75% by weight, more preferably at least 1% by weight, most preferably at least 1.25% by weight and in particular at least 1.5% by weight, based on the amount of polyurethane (A).

Der Gehalt an Wasser beträgt bevorzugt bis zu 3,5 Gew%, besonders bevorzugt bis zu 3 Gew%, bezogen auf die Menge Polyurethan (A).The content of water is preferably up to 3.5% by weight, more preferably up to 3% by weight, based on the amount of polyurethane (A).

Diese Formulierungen sind in der Regel lagerstabil und entmischen sich nicht.These formulations are usually storage stable and do not segregate.

Es stellt einen Vorteil dieser Formulierungen dar, daß durch die Beimischung der genannten Menge Wasser die Viskosität des Polyurethans (A) verringert werden kann. In der Regel beträgt die Viskosität gemessen gemäß DIN EN ISO 3219 (Scherrate D, 100 s-1) bei 23°C nicht mehr als 400 Pas, so daß die Formulierung fließfähig ist. Bevorzugt beträgt die Viskosität weniger als 300, besonders bevorzugt weniger als 250 Pas und ganz besonders bevorzugt weniger als 200 Pas.It is an advantage of these formulations that the viscosity of the polyurethane (A) can be reduced by adding said amount of water. As a rule, the viscosity measured in accordance with DIN EN ISO 3219 (shear rate D, 100 s -1 ) at 23 ° C. is not more than 400 Pas, so that the formulation is free-flowing. The viscosity is preferably less than 300, more preferably less than 250 Pas and most preferably less than 200 Pas.

Die Formulierung kann als Lösung oder Dispersion vorliegen, bevorzugt als Lösung von Wasser in dem Polyurethan (A). Zur Vermischung wird die Menge Wasser gegebenenfalls portionsweise in das Polyurethan (A) unter Energieeintrag eingetragen. Es ist jedoch auch möglich, daß das Polyurethan (A) zu Wasser hinzugegeben wird.
Die Vermischung kann beispielsweise durch Rühren, statische Mischer oder Ultraschall erfolgen, bevorzugt durch Rühren.The formulation may be in the form of a solution or dispersion, preferably as a solution of water in the polyurethane (A). For mixing, the amount of water is optionally added in portions in the polyurethane (A) with input of energy. However, it is also possible that the polyurethane (A) is added to water.
The mixing can be carried out, for example, by stirring, static mixers or ultrasound, preferably by stirring.

Die Polyurethane (A) und die erfindungsgemäßen Formulierungen von einbaubaren Photoinitiatoren können bevorzugt in erfindungsgemäßen Tinten, Druckfarben und Drucklacken eingesetzt werden.The polyurethanes (A) and the formulations of incorporable photoinitiators according to the invention can preferably be used in inks, printing inks and printing varnishes according to the invention.

Ein weiterer Gegenstand der vorliegenden Erfindung sind Tinten, Druckfarben und Drucklacke, enthaltend
mindestens ein Polyurethan A, enthaltend als Aufbaukomponenten

  1. (a) mindestens ein organisches aliphatisches, aromatisches oder cycloaliphatisches Di- oder Polyisocyanat mit einer Funktionalität von mehr als 2,
  2. (b) mindestens eine Verbindung mit jeweils mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren ungesättigten Gruppe,
  3. (c) mindestens einen Photoinitiator mit mindestens einer gegenüber Isocyanat reaktiven Gruppe,
  4. (d) gegebenenfalls mindestens ein weiteres Di- und/oder Polyisocyanat, das von der Verbindung (a) verschieden ist,
  5. (e) gegebenenfalls mindestens eine Verbindung mit mindestens zwei gegenüber Isocyanat reaktiven Gruppen,
  6. (f) gegebenenfalls mindestens eine Verbindung mit genau einer gegenüber Isocyanat reaktiven Gruppe
sowie zusätzlich zum Polyurethan (A)
0,5 bis 4 Gew% Wasser, bezogen auf die Menge Polyurethan (A),
optional mindestens ein Pigment,
mindestens eine multifunktionelle polymerisationsfähige Verbindung (B),
optional mindestens einen weiteren Photoinitiator, sowie
optional druckfarbentypische Additive.Another object of the present invention are inks, inks and printing varnish containing
at least one polyurethane A, containing as structural components
  1. (a) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate having a functionality of more than 2,
  2. (b) at least one compound having in each case at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group,
  3. (c) at least one photoinitiator having at least one isocyanate-reactive group,
  4. (d) optionally, at least one further di- and / or polyisocyanate other than compound (a),
  5. (e) optionally, at least one compound having at least two isocyanate-reactive groups,
  6. (f) optionally at least one compound having exactly one isocyanate-reactive group
and in addition to the polyurethane (A)
0.5 to 4% by weight of water, based on the amount of polyurethane (A),
optionally at least one pigment,
at least one multifunctional polymerizable compound (B),
optionally at least one further photoinitiator, as well
optional printing inks typical additives.

Die erfindungsgemäßen Drucklacke enthalten kein Pigment.The printing lacquers of the invention contain no pigment.

Der mindestens eine weitere Photoinitiator ist bevorzugt anwesend bei pigmentierten Druckfarben und bei Drucklacken.The at least one further photoinitiator is preferably present in pigmented printing inks and printing inks.

Unter dem Begriff "Druckfarbe" wird in dieser Anmeldung als Sammelbezeichnung für farbmittelhaltige Zubereitungen mit unterschiedlicher Konsistenz, die ausschließlich mittels einer Druckform auf einen Bedruckstoff übertragen und dort als Farbfilm (Druck) fixiert werden (CEPE-Definition).The term "printing ink" is used in this application as a collective name for colorant-containing preparations with different consistency, which are transferred exclusively by means of a printing plate on a substrate and there fixed as a color film (pressure) (CEPE definition).

Dem deutschen Sprachgebrauch folgend wird der Begriff "Tinte" in dieser Anmeldung ausschließlich für Farbflüssigkeiten für Ink-Jet-Flüssigkeit sowie für Flüssigtoner für elektrophotographische Druckverfahren verwendet.As used in the art, the term "ink" in this application is used solely for ink jet ink liquid liquids and liquid toner for electrophotographic printing processes.

Die erfindungsgemäßen Tinten, Druckfarben und Drucklacke können verwendet werden zum Bedrucken von verschiedenen Substraten, bevorzugt Polyamiden, Polethylen, Polypropylen, Polyestern, Poylethylenterephthalat, Polystyrol, Papier, Pappe, Karton, kunststoffbeschichtetes Papier, kunststoffbeschichtete Pappe oder kunststoffbeschichteter Karton, Aluminium und aluminiumbeschichteten Kunststofffolien, bevorzugt von Polethylen, Polypropylen und Polyestern sowie Papier und KartonThe inks, printing inks and printing varnishes according to the invention can be used for printing on various substrates, preferably polyamides, polyethylene, polypropylene, polyesters, polyethylene terephthalate, polystyrene, paper, cardboard, cardboard, plastic-coated paper, plastic-coated cardboard or plastic-coated cardboard, aluminum and aluminum-coated plastic films of polyethylene, polypropylene and polyesters as well as paper and cardboard

Sind Papier, Pappe oder Karton kunststoffbeschichtet, so handelt es sich bei dem Kunststoff bevorzugt um Polyolefine, besonders bevorzugt um Polyethylen oder Polypropylen.If paper, cardboard or cardboard are plastic-coated, then the plastic is preferably polyolefins, more preferably polyethylene or polypropylene.

Die so bedruckten Substrate sind insbesondere geeignet als Verpackungsmaterialien für Lebensmittel, Kosmetik und Arzneimittel.The substrates thus printed are particularly suitable as packaging materials for food, cosmetics and pharmaceuticals.

Die erfindungsgemäßen Polyurethane (A) können als alleiniges Bindemittel oder bevorzugt in Kombination mit mindestens einer weiteren radikalisch polymerisierbaren Verbindung verwendet werden.The polyurethanes (A) according to the invention can be used as the sole binder or, preferably, in combination with at least one further free-radically polymerizable compound.

Radikalisch polymerisationsfähige Gruppen sind beispielsweise bevorzugt (Meth)Acrylat-Gruppen und besonders bevorzugt Acrylat-Gruppen.Radical polymerizable groups are for example preferred (meth) acrylate groups and more preferably acrylate groups.

Bei den radikalisch polymerisationsfähige Verbindungen (B) handelt es sich bevorzugt um multifunktionelle (Verbindung mit mehr als einer radikalisch polymerisierbaren Doppelbindung) polymerisationsfähige Verbindungen.The free-radically polymerizable compounds (B) are preferably polyfunctional compounds (compounds having more than one free-radically polymerizable double bond) that can be polymerized.

(Meth)Acrylsäure steht in dieser Schrift für Methacrylsäure und Acrylsäure, bevorzugt für Acrylsäure.(Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.

Multifunktionelle, polymerisationsfähige Verbindungen sind bevorzugt multifunktionelle (Meth)acrylate, die mindestens 2, bevorzugt 2-10, besonders bevorzugt 3 - 6 und ganz besonders bevorzugt 3 - 4 (Meth)acrylatgruppen, bevorzugt Acrylatgruppen tragen.Multifunctional, polymerizable compounds are preferably multifunctional (meth) acrylates which carry at least 2, preferably 2-10, more preferably 3-6 and most preferably 3-4 (meth) acrylate groups, preferably acrylate groups.

Beispiele für multifunktionelle, polymerisationsfähige Verbindungen sind Ethylenglykoldiacrylat, 1,2-Propandioldiacrylat, 1,3-Propandioldiacrylat, 1,4-Butandioldiacrylat, 1,3-Butandioldiacrylat, 1,5-Pentandioldiacrylat, 1,6-Hexandioldiacrylat, 1,8-Octandioldiacrylat, Neopentylglykoldiacrylat, 1,1-, 1,2-, 1,3- und 1,4-Cyclohexandimethanoldiacrylat, 1,2-, 1,3- oder 1,4-Cyclohexandioldiacrylat, Diproyplengylkoldiacrylat,Tripropylenglykoldiacrylat, Trimethylolpropantriacrylat, Ditrimethylolpropantetraacrylat, Dipentaerythritpenta- oder -hexaacrylat, Pentaerythrittri- oder -tetraacrylat, Glycerindi- oder - triacrylat, sowie Di- und Polyacrylate von Zuckeralkoholen, wie beispielsweise Sorbit, Mannit, Diglycerol, Threit, Erythrit, Adonit (Ribit), Arabit (Lyxit), Xylit, Dulcit (Galactit), Maltit oder Isomalt, oder von Polyesterpolyolen, Polyetherolen, Poly-THF mit einer Molmasse zwischen 162 und 2000, Poly-1,3-Propandiol mit einer Molmasse zwischen 134 und 1178, Polyethylenglykol mit einer Molmasse zwischen 106 und 898, sowie Epoxy(meth)acrylate, , Polyester(meth)acrylate, Polyether(meth)acrylate, Urethan-(meth)acrylate oder Polycarbonat(meth)acrylate, die optional auch mit einem oder mehreren Aminen modifiziert sein können.Examples of multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate , Neopentyl glycol diacrylate, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol diacrylate, 1,2-, 1,3- or 1,4-cyclohexanediol diacrylate, diproypline glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentahacrylate. or hexaacrylate, pentaerythritol tri- or tetraacrylate, glycerol di- or triacrylate, and di- and polyacrylates of sugar alcohols, such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol ( Galactitol), maltitol or isomalt, or of polyester polyols, polyetherols, poly-THF with a Molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between 134 and 1178, polyethylene glycol with a molecular weight between 106 and 898, and also epoxy (meth) acrylates,, polyester (meth) acrylates, polyether (meth) acrylates, Urethane (meth) acrylates or polycarbonate (meth) acrylates, which may optionally also be modified with one or more amines.

Weitere Beispiele sind (Meth)Acrylate von Verbindungen der Formel (VIIIa) bis (Vllld),

Figure imgb0004
Figure imgb0005
 worin

  • R7 und R8 unabhängig voneinander Wasserstoff oder gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C1 - C18-Alkyl,
  • k, l, m, q unabhängig voneinander je für eine ganze Zahl von 1 bis 10, bevorzugt 1 bis 5 und besonders bevorzugt 1 bis 3 steht und
  • jedes Xi für i = 1 bis k, 1 bis I, 1 bis m und 1 bis q unabhängig voneinander ausgewählt sein kann aus der Gruppe -CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O- und -CHPh-CH2-O-, bevorzugt aus der Gruppe -CH2-CH2-O-, -CH2-CH(CH3)-O- und -CH(CH3)-CH2-O-, und besonders bevorzugt -CH2-CH2-O-,
  • worin Ph für Phenyl und Vin für Vinyl steht.
Further examples are (meth) acrylates of compounds of the formula (VIIIa) to (VIII),
Figure imgb0004
Figure imgb0005
 wherein
  • R 7 and R 8 independently of one another denote hydrogen or C 1 -C 18 -alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
  • k, l, m, q independently of one another are each an integer from 1 to 10, preferably 1 to 5 and particularly preferably 1 to 3, and
  • each X i for i = 1 to k, 1 to I, 1 to m and 1 to q can be independently selected from the group -CH 2 -CH 2 -O-, -CH 2 -CH (CH 3 ) -O -, -CH (CH 3 ) -CH 2 -O-, -CH 2 -C (CH 3 ) 2 -O-, -C (CH 3 ) 2 -CH 2 -O-, -CH 2 -CHVin-O -, -CHVin-CH 2 -O-, -CH 2 -CHPh-O- and -CHPh-CH 2 -O-, preferably from the group -CH 2 -CH 2 -O-, -CH 2 -CH (CH 3 ) -O- and -CH (CH 3 ) -CH 2 -O-, and more preferably -CH 2 -CH 2 -O-,
  • where Ph is phenyl and Vin is vinyl.

Darin bedeuten gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C1 - C18-Alkyl beispielsweise Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, sec-Butyl, tert.-Butyl, Pentyl, Hexyl, Heptyl, Octyl, 2-Etylhexyl, 2,4,4-Trimethylpentyl, Decyl, Dodecyl, Tetradecyl, Hetadecyl, Octadecyl, 1,1-Dimethylpropyl, 1,1-Dimethylbutyl, 1,1,3,3-Tetramethylbutyl, bevorzugt Methyl, Ethyl oder n-Propyl, ganz besonders bevorzugt Methyl oder Ethyl.In this formula, C 1 -C 18 -alkyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl Methyl, ethyl or n-propyl, most preferably methyl or ethyl.

Bevorzugt handelt es sich dabei um (Meth)Acrylate von ein- bis zwanzigfach und besonders bevorzugt drei- bis zehnfach ethoxyliertem, propoxyliertem oder gemischt ethoxyliertem und propoxyliertem und insbesondere ausschließlich ethoxyliertem Neopentylglykol, Trimethylolpropan, Trimethylolethan oder Pentaerythrit.These are preferably (meth) acrylates of one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol.

Bevorzugte multifunktionelle, polymerisationsfähige Verbindungen sind, 1,2-Propandioldiacrylat, 1,3-Propandioldiacrylat, Diproyplengylkoldiacrylat, Tripropylenglykoldiacrylat, Trimethylolpropantriacrylat, Ditrimethyloltetracrylat und Dipentaerithrolhexaacrylat, Polyesterpolyolacrylate, Polyetherolacrylate und Triacrylat von ein- bis zwanzigfach alkoxyliertem, besonders bevorzugt ein- bis 20fach ethoxyliertem Trimethylolpropan, ein- bis 20fach propoxyliertem Glycerin oder ein- bis 20fach ethoxyliertem und/oder propoxyliertem Pentaerythrit.Preferred multifunctional, polymerizable compounds are 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, diproypline glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylol tetracrylate and dipentaerythritol hexaacrylate, polyester polyol acrylates, polyetherol acrylates and triacrylate of one to twenty times alkoxylated, more preferably one to twenty times ethoxylated trimethylolpropane, one to 20 times propoxylated glycerol or one to 20 times ethoxylated and / or propoxylated pentaerythritol.

In einer bevorzugten Ausführungsform werden in Drucklacken Epoxy(meth)acrylate als multifunktionelle, polymerisationsfähige Verbindungen eingesetzt.In a preferred embodiment, epoxy (meth) acrylates are used as multifunctional, polymerizable compounds in printing finishes.

Ganz besonders bevorzugte multifunktionelle, polymerisationsfähige Verbindungen sind Trimethylolpropantriacrylat und Triacrylat von ein- bis zwanzigfach ethoxyliertem Trimethylolpropan, Triacrylat von ein- bis 20fach propoxyliertem Glycerin oder Tetraacrylat von ein- bis 20fach ethoxyliertem und/oder propoxyliertem Pentaerythrit. Weitere Bestandteile können auch teilweise oder vollständig mit (Meth)Acrylsäure veresterte Polyalkohole sein.Very particularly preferred multifunctional, polymerizable compounds are trimethylolpropane triacrylate and triacrylate of one to twenty times ethoxylated trimethylolpropane, triacrylate of one to 20 times propoxylated glycerol or tetraacrylate of one to 20 times ethoxylated and / or propoxylated pentaerythritol. Further constituents may also be partially or completely esterified with (meth) acrylic acid esterified polyalcohols.

Derartige Polyalkohole sind beispielsweise mindestens zweiwertige Polyole, Polyetherole oder Polyesterole oder Polyacrylatpolyole mit einer mittleren OH-Funktionalität von mindestens 2, bevorzugt mindestens 3, besonders bevorzugt mindestens 4 und ganz besonders bevorzugt 4 bis 20.Such polyalcohols are, for example, at least divalent polyols, polyetherols or polyesterols or polyacrylate polyols having an average OH functionality of at least 2, preferably at least 3, more preferably at least 4 and most preferably 4 to 20.

Polyetherole können zusätzlich zu den alkoxylierten Polyolen auch Polyethylenglykol mit einer Molmasse zwischen 106 und 2000, Polypropylenglykol mit einem Molgewicht zwischen 134 und 2000, Poly-THF mit einem Molgewicht zwischen 162 und 2000 oder Poly-1,3-propandiol mit einem Molgewicht zwischen 134 und 400 sein.Polyetherols in addition to the alkoxylated polyols also polyethylene glycol having a molecular weight between 106 and 2000, polypropylene glycol having a molecular weight between 134 and 2000, poly-THF having a molecular weight between 162 and 2000 or poly-1,3-propanediol having a molecular weight between 134 and 400 be.

Polyesterpolyole, sind z.B. aus Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, Band 19, S. 62 bis 65 bekannt. Bevorzugt werden Polyesterpolyole eingesetzt, die durch Umsetzung von zweiwertigen Alkoholen mit zweiwertigen Carbonsäuren erhalten werden. Anstelle der freien Polycarbonsäuren können auch die entsprechenden Polycarbonsäureanhydride oder entsprechende Polycarbonsäureester von niederen Alkoholen oder deren Gemische zur Herstellung der Polyesterpolyole verwendet werden. Die Polycarbonsäuren können aliphatisch, cycloaliphatisch, araliphatisch, aromatisch oder heterocyclisch sein und gegebenenfalls, z.B. durch Halogenatome, substituiert und/oder ungesättigt sein. Als Beispiele hierfür seien genannt:Polyester polyols are, for example Ullmanns Encyklopadie der technischen Chemie, 4th Edition, Volume 19, pp. 62 to 65 known. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids to be obtained. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples include:

Oxalsäure, Maleinsäure, Fumarsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure, Dodekandisäure, o-Phthalsäure, Isophthalsäure, Terephthalsäure, Trimellithsäure, Azelainsäure, 1,4-Cyclohexandicarbonsäure oder Tetrahydrophthalsäure, Korksäure, Azelainsäure, Phthalsäureanhydrid, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäureanhydrid, Tetrachlorphthalsäureanhydrid, Endomethylentetrahydrophthalsäureanhydrid, Glutarsäureanhydrid, Maleinsäureanhydrid, dimere Fettsäuren, deren Isomere und Hydrierungsprodukte sowie veresterbare Derivate, wie Anhydride oder Dialkylester, beispielsweise C1-C4-Alkylester, bevorzugt Methyl-, Ethyl- oder n-Butylester, der genannten Säuren eingesetzt werden. Bevorzugt sind Dicarbonsäuren der allgemeinen Formel HOOC-(CH2)y-COOH, wobei y eine Zahl von 1 bis 20, bevorzugt eine gerade Zahl von 2 bis 20 ist, besonders bevorzugt Bernsteinsäure, Adipinsäure, Sebacinsäure und Dodecandicarbonsäure.Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, suberic, azelaic, phthalic, tetrahydrophthalic, hexahydrophthalic, tetrachlorophthalic, endomethylenetetrahydrophthalic, Glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products and esterifiable derivatives such as anhydrides or dialkyl esters, for example C 1 -C 4 alkyl esters, preferably methyl, ethyl or n-butyl esters, of the acids mentioned are used. Preference is given to dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Als mehrwertige Alkohole kommen zur Herstellung der Polyesterole in Betracht 1,2-Propandiol, Ethylenglykol, 2,2-Dimethyl-1,2-Ethandiol, 1,3-Propandiol, 1,2-Butandiol, 1,3-Butandiol, 1,4-Butandiol, 3-Methylpentan-1,5-diol, 2-Ethylhexan-1,3-diol, 2,4-Diethyloctan-1,3-diol, 1,6-Hexandiol, Polyethylenglykol mit einer Molmasse zwischen 106 und 2000, Polypropylenglykol mit einem Molgewicht zwischen 134 und 2000, Poly-THF mit einem Molgewicht zwischen 162 und 2000, Poly-1,3-propandiol mit einem Molgewicht zwischen 134 und 400, Neopentylglykol, Hydroxypivalinsäureneopentylglykolester, 2-Ethyl-1,3-Propandiol, 2-Methyl-1,3-Propandiol, 2,2-Bis(4-hydroxycyclohexyl)propan, 1,1-, 1,2-, 1,3- und 1,4-Cyclohexandimethanol, 1,2-, 1,3- oder 1,4-Cyclohexandiol, Trimethylolbutan, Trimethylolpropan, Trimethylolethan, Neopentylglykol, Pentaerythrit, Glycerin, Ditrimethylolpropan, Dipentaerythrit, Sorbit, Mannit, Diglycerol, Threit, Erythrit, Adonit (Ribit), Arabit (Lyxit), Xylit, Dulcit (Galactit), Maltit oder Isomalt, die gegebenenfalls wie oben beschrieben alkoxyliert sein können.Suitable polyhydric alcohols for the preparation of the polyesterols are 1,2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, polyethylene glycol having a molecular weight between 106 and 2000 , Polypropylene glycol having a molecular weight between 134 and 2000, poly-THF having a molecular weight between 162 and 2000, poly-1,3-propanediol having a molecular weight between 134 and 400, neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, 1,2-, 1, 3- or 1,4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol) ), Maltitol o the isomalt, which may optionally be alkoxylated as described above.

Bevorzugt sind Alkohole der allgemeinen Formel HO-(CH2)x-OH, wobei x eine Zahl von 1 bis 20, bevorzugt eine gerade Zahl von 2 bis 20 ist. Bevorzugt sind Ethylenglycol, Butan-1,4-diol, Hexan-1,6-diol, Octan-1,8-diol und Dodecan-1,12- diol. Weiterhin bevorzugt ist Neopentylglykol.Alcohols of the general formula HO- (CH 2 ) x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20, are preferred. Preferred are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Further preferred is neopentyl glycol.

Geeignet sind auch Polyesterdiole auf Lacton-Basis, wobei es sich um Homo- oder Mischpolymerisate von Lactonen, bevorzugt um endständige Hydroxylgruppen aufweisende Anlagerungsprodukte von Lactonen an geeignete difunktionelle Startermoleküle handelt. Als Lactone kommen bevorzugt solche in Betracht, die sich von Verbindungen der allgemeinen Formel HO-(CH2)z-COOH ableiten, wobei z eine Zahl von 1 bis 20 ist und ein H-Atom einer Methyleneinheit auch durch einen C1- bis C4-Alkylrest substituiert sein kann. Beispiele sind ε-Caprolacton, β-Propiolacton, gamma-Butyrolacton und/oder Methyl-ε-caprolacton, 4-Hydroxybenzoesäure, 6-Hydroxy-2-naphthalinsäure oder Pivalolacton sowie deren Gemische. Geeignete Starterkomponenten sind z.B. die vorstehend als Aufbaukomponente für die Polyesterpolyole genannten niedermolekularen zweiwertigen Alkohole. Die entsprechenden Polymerisate des ε-Caprolactons sind besonders bevorzugt. Auch niedere Polyesterdiole oder Polyetherdiole können als Starter zur Herstellung der Lacton-Polymerisate eingesetzt sein. Anstelle der Polymerisate von Lactonen können auch die entsprechenden, chemisch äquivalenten Polykondensate der den Lactonen entsprechenden Hydroxycarbonsäuren, eingesetzt werden.Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Preferred lactones are those which are derived from compounds of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit may also be substituted by a C 1 - to C 4 -alkyl radical. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and mixtures thereof. Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.

Ferner kommen auch Polycarbonat-Diole, wie sie z.B. durch Umsetzung von Phosgen mit einem Überschuß von den als Aufbaukomponenten für die Polyesterpolyole genannten niedermolekularen Alkohole erhalten werden können, in Betracht.Also included are polycarbonate diols, e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.

Weiterhin kann es sich bei der multifunktionellen, polymerisationsfähigen Verbindung um Urethan(meth)acrylate, Epoxy(meth)acrylate oder Carbonat(meth)acrylate handeln.Furthermore, the multifunctional, polymerizable compound may be urethane (meth) acrylates, epoxy (meth) acrylates or carbonate (meth) acrylates.

Urethan(meth)acrylate sind z.B. erhältlich durch Umsetzung von Polyisocyanaten mit Hydroxyalkyl(meth)acrylaten und gegebenenfalls Kettenverlängerungsmitteln wie Diolen, Polyolen, Diaminen, Polyaminen oder Dithiolen oder Polythiolen. In Wasser ohne Zusatz von Emulgatoren dispergierbare Urethan(meth)acrylate enthalten zusätzlich noch ionische und/oder nichtionische hydrophile Gruppen, welche z.B. durch Aufbaukomponenten wie Hydroxycarbonsäuren ins Urethan eingebracht werden.Urethane (meth) acrylates are e.g. obtainable by reacting polyisocyanates with hydroxyalkyl (meth) acrylates and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols. In addition, urethane (meth) acrylates dispersible in water without the addition of emulsifiers additionally contain ionic and / or nonionic hydrophilic groups which are present, for example. be incorporated by structural components such as hydroxycarboxylic acids in the urethane.

Derartige Urethan(meth)acrylate enthalten als Aufbaukomponenten im wesentlichen:

  1. (1) mindestens ein organisches aliphatisches, aromatisches oder cycloaliphatisches Di- oder Polyisocyanat,
  2. (2) mindestens eine Verbindung mit mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren ungesättigten Gruppe und
  3. (3) gegebenenfalls mindestens eine Verbindung mit mindestens zwei gegenüber Isocyanat reaktiven Gruppen.
Such urethane (meth) acrylates contain as structural components essentially:
  1. (1) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate,
  2. (2) at least one compound having at least one isocyanate-reactive group and at least one radically polymerizable unsaturated group and
  3. (3) optionally at least one compound having at least two isocyanate-reactive groups.

Die Komponenten (1), (2) und (3) können die gleichen sein, wie oben als Aufbaukomponenten (a), (b) und (e) für die erfindungsgemäßen Polyurethane beschrieben.The components (1), (2) and (3) may be the same as described above as structural components (a), (b) and (e) for the polyurethanes of the invention.

Die Urethan(meth)acrylate haben vorzugsweise ein zahlenmittleres Molgewicht Mn von 500 bis 20 000, insbesondere von 500 bis 10 000 besonders bevorzugt 600 bis 3000 g/mol (bestimmt durch Gelpermeationschromatographie mit Tetrahydrofuran und Polystyrol als Standard).The urethane (meth) acrylates preferably have a number average molecular weight M n from 500 to 20,000, in particular 500 to 10000 more preferably 600 to 3000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

Die Urethan(meth)acrylate haben vorzugsweise einen Gehalt von 1 bis 5, besonders bevorzugt von 2 bis 4 Mol (Meth)acrylgruppen pro 1000 g Urethan(meth)acrylat.The urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably 2 to 4 moles of (meth) acrylic groups per 1000 g of urethane (meth) acrylate.

Epoxid(meth)acrylate sind erhältlich durch Umsetzung von Epoxiden mit (Meth)acrylsäure. Als Epoxide in Betracht kommen z.B epoxidierte Olefine, aromatische Glycidylether oder aliphatische Glycidylether, bevorzugt solche von aromatischen oder aliphatischen Glycidylethern.Epoxy (meth) acrylates are obtainable by reacting epoxides with (meth) acrylic acid. Suitable epoxides are, for example, epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.

Epoxidierte Olefine können beispielsweise sein Ethylenoxid, Propylenoxid, iso-Butylenoxid, 1-Butenoxid, 2-Butenoxid, Vinyloxiran, Styroloxid oder Epichlorhydrin, bevorzugt sind Ethylenoxid, Propylenoxid, iso-Butylenoxid, Vinyloxiran, Styroloxid oder Epichlorhydrin, besonders bevorzugt Ethylenoxid, Propylenoxid oder Epichlorhydrin und ganz besonders bevorzugt Ethylenoxid und Epichlorhydrin.Epoxidized olefins may be, for example, ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, vinyl oxirane, styrene oxide or epichlorohydrin. Preferred are ethylene oxide, propylene oxide, isobutylene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, particularly preferably ethylene oxide, propylene oxide or epichlorohydrin and most preferably ethylene oxide and epichlorohydrin.

Aromatische Glycidylether sind z.B. Bisphenol-A-diglycidylether, Bisphenol-F-diglycidylether, Bisphenol-B-diglycidylether, Bisphenol-S-diglycidylether, Hydrochinondiglycidylether, Alkylierungsprodukte von Phenol/Dicyclopentadien, z.B. 2,5-bis[(2,3-E-poxypropoxy)phenyl]octahydro-4,7-methano-5H-inden) (CAS-Nr. [13446-85-0]), Tris[4-(2,3-epoxypropoxy)phenyl]methan Isomere)CAS-Nr. [66072-39-7]), Phenol basierte Epoxy Novolake (CAS-Nr. [9003-35-4]) und Kresol basierte Epoxy Novolake (CAS-Nr. [37382-79-9]).Aromatic glycidyl ethers are e.g. Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, e.g. 2,5-bis [(2,3-E-poxypropoxy) phenyl] octahydro-4,7-methano-5H-indene (CAS No. [13446-85-0]), tris [4- (2, 3-epoxypropoxy) phenyl] methane isomers) CAS-No. [66072-39-7]), phenol based epoxy novolacs (CAS # [9003-35-4]) and cresol based epoxy novolacs (CAS # [37382-79-9]).

Aliphatische Glycidylether sind beispielsweise 1,4-Butandioldiglycidether, 1,6-Hexandioldiglycidylether, Trimethylolpropantriglycidylether, Pentaerythrittetraglycidylether, 1,1,2,2-tetrakis[4-(2,3-epoxypropoxy)phenyl]ethan (CAS-Nr. [27043-37-4]), Diglycidylether von Polypropylenglykol (α,ω-bis(2,3-epoxypropoxy)poly(oxypropylen) (CAS-Nr. [16096-30-3]) und von hydriertem Bisphenol A (2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propan, CAS-Nr. [13410-58-7]).Aliphatic glycidyl ethers are, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane (CAS No. [27043] 37-4]), diglycidyl ethers of polypropylene glycol (α, ω-bis (2,3-epoxypropoxy) poly (oxypropylene) (CAS No. [16096-30-3]) and hydrogenated bisphenol A (2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, CAS No. [13410-58-7]).

Die Epoxid(meth)acrylate haben vorzugsweise ein zahlenmittleres Molgewicht Mn von 200 bis 20000, besonders bevorzugt von 200 bis 10000 g/mol und ganz besonders bevorzugt von 250 bis 3000 g/mol; der Gehalt an (Meth)acrylgruppen beträgt vorzugsweise 1 bis 5, besonders bevorzugt 2 bis 4 pro 1000 g Epoxid(meth)acrylat (bestimmt durch Gelpermeationschromatographie mit Polystyrol als Standard und Tetrahydrofuran als Elutionsmittel).The epoxide (meth) acrylates preferably have a number-average molecular weight M n of from 200 to 20 000, particularly preferably from 200 to 10 000 g / mol and very particularly preferably from 250 to 3000 g / mol; the content of (meth) acrylic groups is preferably 1 to 5, more preferably 2 to 4 per 1000 g of epoxy (meth) acrylate (determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).

Carbonat(meth)acrylate enthalten im Mittel vorzugsweise 1 bis 5, insbesondere 2 bis 4, besonders bevorzugt 2 bis 3 (Meth)acrylgruppen und ganz besonders bevorzugt 2(Meth)acrylgruppen.On average, carbonate (meth) acrylates preferably contain 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.

Das zahlenmittlere Molekulargewicht Mn der Carbonat(meth)acrylate ist vorzugsweise kleiner 3000 g/mol, besonders bevorzugt kleiner 1500 g/mol, besonders bevorzugt kleiner 800 g/mol (bestimmt durch Gelpermeationschromatgraphie mit Polystyrol als Standard, Lösemittel Tetrahydrofuran).The number average molecular weight M n of the carbonate (meth) acrylates is preferably less than 3000 g / mol, more preferably less than 1500 g / mol, more preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).

Die Carbonat(meth)acrylate sind in einfacher Weise erhältlich durch Umesterung von Kohlensäureestern mit mehrwertigen, vorzugsweise zweiwertigen Alkoholen (Diolen, z.B. Hexandiol) und anschließende Veresterung der freien OH-Gruppen mit (Meth)acrylsäure oder auch Umesterung mit (Meth)acrylsäureestern, wie es z.B. in EP-A 92 269 beschrieben ist. Erhältlich sind sie auch durch Umsetzung von Phosgen, Harnstoffderivaten mit mehrwertigen, z.B. zweiwertigen Alkoholen.The carbonate (meth) acrylates are obtainable in a simple manner by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, eg hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or else transesterification with (meth) acrylic esters, such as it eg in EP-A 92 269 is described. They are also available by reacting phosgene, urea derivatives with polyhydric, for example dihydric alcohols.

Denkbar sind auch (Meth)acrylate von Polycarbonatpolyolen, wie das Reaktionsprodukt aus einem der genannten Di- oder Polyole und einem Kohlensäureester sowie einem hydroxylgruppenhaltigen (Meth)acrylat.Also conceivable are (meth) acrylates of polycarbonate polyols, such as the reaction product of one of said diols or polyols and a carbonic acid ester and a hydroxyl-containing (meth) acrylate.

Geeignete Kohlensäureester sind z.B. Ethylen-, 1,2- oder 1,3-Propylencarbonat, Kohlensäuredimethyl-, -diethyl- oder -dibutylester.Suitable carbonic acid esters are e.g. Ethylene, 1,2 or 1,3-propylene carbonate, carbonic acid dimethyl, diethyl or dibutyl ester.

Geeignete hydroxygruppenhaltige (Meth)acrylate sind beispielsweise 2-Hydroxyethyl-(meth)acrylat, 2- oder 3-Hydroxypropyl(meth)acrylat, 1,4-Butandiolmono(meth)acrylat, Neopentylglykolmono(meth)acrylat, Glycerinmono- und di(meth)acrylat, Trimethylolpropanmono- und di(meth)acrylat sowie Pentaerythritmono-, -di- und -tri(meth)acrylat.Suitable hydroxyl-containing (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth ) acrylate, trimethylolpropane mono- and di (meth) acrylate and pentaerythritol mono-, di- and tri (meth) acrylate.

Besonders bevorzugte Carbonat(meth)acrylate sind solche der Formel:

Figure imgb0006
worin R für H oder CH3, X für eine C2-C18 Alkylengruppe und n für eine ganze Zahl von 1 bis 5, vorzugsweise 1 bis 3 steht.Particularly preferred carbonate (meth) acrylates are those of the formula:
Figure imgb0006
 wherein R is H or CH 3 , X is a C 2 -C 18 alkylene group and n is an integer from 1 to 5, preferably 1 to 3.

R steht vorzugsweise für H und X steht vorzugsweise für C2- bis C10-Alkylen, beispielsweise 1,2-Ethylen, 1,2-Propylen, 1,3-Propylen, 1,4-Butylen oder 1,6-Hexylen, besonders bevorzugt für C4- bis C8-Alkylen. Ganz besonders bevorzugt steht X für C6-Alkylen.R is preferably H and X is preferably C 2 -C 10 -alkylene, for example 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene or 1,6-hexylene, particularly preferred for C 4 - to C 8 -alkylene. Most preferably, X is C 6 alkylene.

Vorzugsweise handelt es sich bei den Carbonat(meth)acrylaten um aliphatische Carbonat(meth)acrylate.Preferably, the carbonate (meth) acrylates are aliphatic carbonate (meth) acrylates.

Unter den multifunktionellen, polymerisationsfähigen Verbindung sind Urethan(meth)-acrylate besonders bevorzugt.Among the multifunctional polymerizable compound, urethane (meth) acrylates are particularly preferred.

Es kann sinnvoll sein, den erfindungsgemäßen Tinten, Druckfarben und Drucklacken zusätzlich zu dem Polyurethan (A) zusätzlich Photoinitiator zuzusetzen, bevorzugt Photoinitiator, der ein anderes Absorptionsmaximum als die Komponente (c) aufweist.It may be useful to additionally add photoinitiator to the inks, printing inks and printing varnishes according to the invention in addition to the polyurethane (A), preferably a photoinitiator which has a different absorption maximum than component (c).

Photoinitiatoren können beispielsweise dem Fachmann bekannte Photoinitiatoren sein, z.B. solche in " Advances in Polymer Science", Volume 14, Springer Berlin 1974 oder in K. K. Dietliker, Chemistry and Technology of UV- and EB-Formulation for Coatings, Inks and Paints, Volume 3 ; Photoinitiators for Free Radical and Cationic Polymerization, P. K. T. Oldring (Eds), SITA Technology Ltd, London, genannt en.Photoinitiators may be, for example, photoinitiators known to the person skilled in the art, for example those in " Advances in Polymer Science ", Volume 14, Springer Berlin 1974 or in KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3 ; Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London s.

In Betracht kommen z.B. Mono- oder Bisacylphosphinoxide, wie sie z.B. in EP-A 7 508 , EP-A 57 474 , DE-A 196 18 720 , EP-A 495 751 oder EP-A 615 980 beschrieben sind, beispielsweise 2,4,6-Trimethylbenzoyldiphenylphosphinoxid (Lucirin® TPO der BASF SE), Ethyl-2,4,6-trimethylbenzoylphenylphosphinat (Lucirin® TPO L der BASF SE), Bis-(2,4,6-trimethylbenzoyl)-phenylphosphinoxid (Irgacure® 819 der BASF SE), Benzophenone, Hydroxyacetophenone, Phenylglyoxylsäure und ihre Derivate oder Gemische dieser Photoinitiatoren. Als Beispiele seien genannt Benzophenon, Acetophenon, Acetonaphthochinon, Methylethylketon, Valerophenon, Hexanophenon, α-Phenylbutyrophenon, p-Morpholinopropiophenon, Dibenzosuberon, 4-Morpholinobenzophenon, 4-Morpholinodeoxybenzoin, p-Diacetylbenzol, 4-Aminobenzophenon, 4'-Methoxyacetophenon, β-Methylanthrachinon, tert-Butylanthrachinon, Anthrachinoncarbonysäureester, Benzaldehyd, α-Tetralon, 9-Acetylphenanthren, 2-Acetylphenanthren, 10-Thioxanthon, 3-Acetylphenanthren, 3-Acetylindol, 9-Fluorenon, 1-Indanon, 1,3,4-Triacetylbenzol, Thioxanthen-9-on, Xanthen-9-on, 2,4-Dimethylthioxanthon, 2,4-Diethylthioxanthon, 2,4-Di-iso-propylthioxanthon, 2,4-Dichlorthioxanthon, Benzoin, Benzoin-iso-butylether, Chloroxanthenon, Benzoin-tetrahydropyranylether, Benzoin-methylether, Benzoin-ethylether, Benzoin-butylether, Benzoin-iso-propylether, 7-H-Benzoin-methylether, Benz[de]anthracen-7-on, 1-Naphthaldehyd, 4,4'-Bis(dimethylamino)benzophenon, 4-Phenylbenzophenon, 4-Chlorbenzophenon, Michlers Keton, 1-Acetonaphthon, 2-Acetonaphthon, 1-Benzoylcyclohexan-1-ol, 2-Hydroxy-2,2-dimethylacetophenon, 2,2-Dimethoxy-2-phenylacetophenon, 2,2-Diethoxy-2-phenylacetophenon, 1,1-Dichloracetophenon, 1-Hydroxyacetophenon, Acetophenondimethylketal, o-Methoxybenzophenon, 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methyl-propanoyl)phenyl]methyl]phenyl]-2-methyl-propan-1-on,2-Benzyl-2-dimethylamino-4'-morpholinobutyrophenon, 2-(Dimethylamino)-1-(4-morpholinophenyl)-2-(p-tolylmethyl)butan-1-on, 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-on, Triphenylphosphin, Tri-o-Tolylphosphin, Benz[a]anthracen-7,12-dion, 2,2-Diethoxyacetophenon, Benzilketale, wie Benzildimethylketal, Anthrachinone wie 2-Methylanthrachinon, 2-Ethylanthrachinon, 2-tert-Butyl-anthrachinon, 1-Chloranthrachinon, 2-Amylanthrachinon und 2,3-Butandion.Suitable examples include mono- or Bisacylphosphinoxide, as they are eg in EP-A 7 508 . EP-A 57 474 . DE-A 196 18 720 . EP-A 495 751 or EP-A 615 980 For example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO from BASF SE), ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin® TPO L from BASF SE), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure® 819 from BASF SE), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and its derivatives or mixtures of these photoinitiators. Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, β-methylanthraquinone , tert -butylanthraquinone, anthraquinone carboxylic acid ester, benzaldehyde, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,4-triacetylbenzene, thioxanthene -9-one, xanthene-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di- iso -propylthioxanthon, 2,4-dichlorothioxanthone, benzoin, benzoin iso-butyl ether, Chloroxanthenon, benzoin tetrahydropyranyl ethers, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, 7-H-benzoin methyl ether, benz [de] anthracen-7-one, 1-naphthaldehyde, 4,4'-bis ( dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Mich The ketone, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1 , 1-dichloroacetophenone, 1-hydroxyacetophenone, acetophenone dimethyl ketal, o-methoxybenzophenone, 2-hydroxy-1- [4 - [[4- (2-hydroxy-2-methylpropanoyl) phenyl] methyl] phenyl] -2-methyl- propan-1-one, 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2- (p-tolylmethyl) butan-1-one, 2-methyl 1- (4-methylthiophenyl) -2-morpholinopropan-1-one, triphenylphosphine, tri-o-tolylphosphine, benz [a] anthracene-7,12-dione, 2,2-diethoxyacetophenone, benzil ketals such as benzil dimethyl ketal, anthraquinones such as 2 -Methylanthraquinone, 2-ethylanthraquinone, 2- tert- butyl anthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2,3-butanedione.

Denkbar als Photoinitiatoren sind ebenfalls polymere Photoinitiatoren, wie beispielsweise der Diester von Carboxymethoxybenzophenon mit Polytetramethylenglykolen unterschiedlichen Molgewichts, bevorzugt 200 bis 250 g/mol ( CAS 515136-48-8 ), sowie CAS 1246194-73-9 , CAS 813452-37-8 , CAS 71512-90-8 , CAS 886463-10-1 oder weitere polymere Benzophenonderivate, wie sie beispielsweise unter dem Handelsnamen Omnipol® BP der Firma IGM Resins B.V., Waalwijk, Niederlande oder Genopol® BP1 der Firma Rahn AG, Schweiz im Handel verfügbar sind. Denkbar sind ferner auch polymere Thioxanthone, beispielsweise der Diester von Carboxymethoxythioxanthonen mit Polytetramethylenglykolen unterschiedlichen Molgewichts, wie sie beispielsweise unter dem Handelsnamen Omnipol® TX der Firma IGM Resins B.V., Waalwijk, Niederlande im Handel verfügbar sind. Denkbar sind ferner auch polymere α-Aminoketone, beispielsweise der Diester von Carboxyethoxythioxanthonen mit Polyethylenglykolen unterschiedlichen Molgewichts, wie sie beispielsweise unter dem Handelsnamen Omnipol® 910 oder Omnipol® 9210 der Firma IGM Resins B.V., Waalwijk, Niederlande im Handel verfügbar sind.Also conceivable as photoinitiators are polymeric photoinitiators, such as, for example, the diester of carboxymethoxybenzophenone with polytetramethylene glycols of different molecular weight, preferably 200 to 250 g / mol ( CAS 515136-48-8 ), such as CAS 1246194-73-9 . CAS 813452-37-8 . CAS 71512-90-8 . CAS 886463-10-1 or other polymeric benzophenone derivatives, such as those commercially available, for example, under the trade name Omnipol® BP from IGM Resins BV, Waalwijk, Netherlands or Genopol® BP1 from Rahn AG, Switzerland. Also conceivable are polymeric thioxanthones, for example the diesters of carboxymethoxythioxanthones with polytetramethylene glycols of different molecular weight, such as are commercially available, for example, under the trade name Omnipol® TX from IGM Resins BV, Waalwijk, the Netherlands. Also conceivable are polymeric α-aminoketones, for example the diesters of carboxyethoxythioxanthones with polyethylene glycols of different molecular weight, such as are commercially available, for example, under the trade name Omnipol® 910 or Omnipol® 9210 from IGM Resins BV, Waalwijk, the Netherlands.

In einer bevorzugten Ausführungsform werden als Photoinitiatoren Silsesquioxanverbindungen mit mindestens einer initiierend wirkenden Gruppe eingesetzt, wie sie beschrieben sind in WO 2010/063612 A1 , dort besonders von Seite 2, Zeile 21 bis Seite 43, Zeile 9, was hiermit per Bezugnahme Bestandteil der vorliegenden Offenbarung sei, bevorzugt von Seite 2, Zeile 21 bis Seite 30, Zeile 5 sowie den in den Beispiele der WO 2010/063612 A1 beschriebenen Verbindungen.In a preferred embodiment, silsesquioxane compounds having at least one initiating group as described are used as photoinitiators WO 2010/063612 A1 there especially from page 2, line 21 to page 43, line 9, which is hereby incorporated by reference into the present disclosure, preferably from page 2, line 21 to page 30, line 5 and in the examples of WO 2010/063612 A1 described compounds.

Geeignet sind auch nicht- oder wenig vergilbende Photoinitiatoren vom Phenylglyoxalsäureestertyp, wie in DE-A 198 26 712 , DE-A 199 13 353 oder WO 98/33761 beschriebene Silsesquioxanverbindungen.Also suitable are non- or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type, as in DE-A 198 26 712 . DE-A 199 13 353 or WO 98/33761 described silsesquioxane compounds.

Bevorzugt unter diesen Photoinitiatoren sind 2,4,6-Trimethylbenzoyldiphenylphosphinoxid, Ethyl-2,4,6-trimethylbenzoylphenylphosphinat, Bis-(2,4,6-trimethylbenzoyl)-phenylphosphinoxid, 2-Benzyl-2-dimethylamino-4'-morpholinobutyrophenon, 2-(Dimethylamino)-1-(4-morpholinophenyl)-2-(p-tolylmethyl)butan-1-on, 2-Hydroxy-1-[4-[[4-(2-hydroxy-2-methyl-propanoyl)phenyl]methyl]phenyl]-2-methyl-propan-1-on sowie die oben beschriebenen polymeren Thioxanthon- und Benzophenonderivate sowie die in WO 2010/063612 A1 beschriebenen.Preferred among these photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, 2- (Dimethylamino) -1- (4-morpholinophenyl) -2- (p-tolylmethyl) butan-1-one, 2-hydroxy-1- [4 - [[4- (2-hydroxy-2-methylpropanoyl ) phenyl] methyl] phenyl] -2-methyl-propan-1-one and the above-described polymeric thioxanthone and benzophenone derivatives and the in WO 2010/063612 A1 described.

Als weitere druckfarbentypische Additive können beispielsweise Dispergiermittel, Wachse, Stabilisatoren, Sensibilisatoren, Füllmittel, Entschäumer, Farbstoffe, antistatische Agentien, Verdicker, oberflächenaktive Agentien wie Verlaufsmittel, Slip-aids oder Haftvermittler verwendet werden.As further typical additives for printing inks, for example dispersants, waxes, stabilizers, sensitizers, fillers, defoamers, dyes, antistatic agents, thickeners, surface-active agents such as leveling agents, slip aids or adhesion promoters can be used.

Geeignete Füllstoffe umfassen Silikate, z. B. durch Hydrolyse von Siliciumtetrachlorid erhältliche Silikate wie Aerosil® der Fa. Degussa, Kieselerde, Talkum, Aluminiumsilikate, Magnesiumsilikate, Calciumcarbonate etc.Suitable fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.

Im Folgenden sind Beispiele für besonders gut geeignete Pigmente genannt.The following are examples of particularly suitable pigments.

Organische Pigmente:Organic pigments:

  • Monoazopigmente:    C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36 und 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, 53:1, 53:3, 57:1, 63, 112, 146, 170, 184, 210, 245 und 251; C.I. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 und 183;Monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36 and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; C.I. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;
  • Disazopigmente:    C.I. Pigment Orange 16, 34 und 44; C.I. Pigment Red 144, 166, 214 und 242; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 und 188;Disazo pigments: C.I. Pigment Orange 16, 34 and 44; C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;
  • Anthanthronpigmente:    C.I. Pigment Red 168 (C.I. Vat Orange 3);Anthanthrone pigments: C.I. Pigment Red 168 (C.I. Vat Orange 3);
  • Anthrachinonpigmente:    C.I. Pigment Yellow 147 und 177; C.I. Pigment Violet 31;Anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31;
  • Anthrachinonpigmente:    C.I. Pigment Yellow 147 und 177; C.I. Pigment Violet 31;Anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31;
  • Anthrapyrimidinpigmente:    C.I. Pigment Yellow 108 (C.I. Vat Yellow 20);Anthrapyrimidine pigments: C.I. Pigment Yellow 108 (C.I. Vat Yellow 20);
  • Chinacridonpigmente:    C.I. Pigment Red 122, 202 und 206; C.I. Pigment Violet 19;Quinacridone pigments: C.I. Pigment Red 122, 202 and 206; C.I. Pigment Violet 19;
  • Chinophthalonpigmente:    C.I. Pigment Yellow 138;Quinophthalone pigments: C.I. Pigment Yellow 138;
  • Dioxazinpigmente:    C.I. Pigment Violet 23 und 37;Dioxazine pigments: C.I. Pigment Violet 23 and 37;
  • Flavanthronpigmente:    C.I. Pigment Yellow 24 (C.I. Vat Yellow 1);Flavanthrone pigments: C.I. Pigment Yellow 24 (C.I. Vat Yellow 1);
  • Indanthronpigmente:    C.I. Pigment Blue 60 (C.I. Vat Blue 4) und 64 (C.I. Vat Blue 6);Indanthrone pigments: C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64 (C.I. Vat Blue 6);
  • Isoindolinpigmente:    C.I. Pigment Orange 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 und 185;Isoindoline pigments: C.I. Pigment Orange 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 and 185;
  • Isoindolinonpigmente:    C.I. Pigment Orange 61; C.I. Pigment Red 257 und 260; C.I. Pigment Yellow 109, 110, 173 und 185;Isoindolinone pigments: C.I. Pigment Orange 61; C.I. Pigment Red 257 and 260; C.I. Pigment Yellow 109, 110, 173 and 185;
  • Isoviolanthronpigmente:    C.I. Pigment Violet 31 (C.I. Vat Violet 1);Isoviolanthrone pigments: C.I. Pigment Violet 31 (C. I. Vat Violet 1);
  • Metallkomplexpigmente:    C.I. Pigment Yellow 117, 150 und 153; C.I. Pigment Green 8;Metal Complex Pigments: C.I. Pigment Yellow 117, 150 and 153; C.I. Pigment Green 8;
  • Perinonpigmente:    C.I. Pigment Orange 43 (C.I. Vat Orange 7); C.I. Pigment Red 194 (C.I. Vat Red 15);Perinone pigments: C.I. Pigment Orange 43 (C.I. Vat Orange 7); C.I. Pigment Red 194 (C.I., Vat Red 15);
  • Perylenpigmente:    C.I. Pigment Black 31 und 32; C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23), 190 (C.I. Vat Red 29) und 224; C.I. Pigment Violet 29;Perylene pigments: C.I. Pigment Black 31 and 32; C.I. Pigment Red 123, 149, 178, 179 (C.I., Vat Red 23), 190 (C.I., Vat Red 29) and 224; C.I. Pigment Violet 29;
  • Phthalocyaninpigmente:    C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 und 16; C.I. Pigment Green 7 und 36;Phthalocyanine pigments: C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; C.I. Pigment Green 7 and 36;
  • Pyranthronpigmente:     C.I. Pigment Orange 51; C.I. Pigment Red 216 (C.I. Vat Orange 4);Pyranthrone pigments: C.I. Pigment Orange 51; C.I. Pigment Red 216 (C.I. Vat Orange 4);
  • Thioindigopigmente:    C.I. Pigment Red 88 und 181 (C.I. Vat Red 1); C.I. Pigment Violet 38 (C.I. Vat Violet 3);Thioindigo pigments: CI Pigment Red 88 and 181 (CI Vat Red 1); CI Pigment Violet 38 (CI Vat Violet 3);
  • Triarylcarboniumpigmente:    C.I. Pigment Blue 1, 61 und 62; C.I. Pigment Green 1; C.I. Pigment Red 81, 81:1 und 169; C.I. Pigment Violet 1, 2, 3 und 27; C.I. Pigment Black 1 (Anilinschwarz); C.I. Pigment Yellow 101 (Aldazingelb); C.I. Pigment Brown 22.Triaryl carbonium pigments: C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment Red 81, 81: 1 and 169; C.I. Pigment Violet 1, 2, 3 and 27; C.I. Pigment Black 1 (aniline black); C.I. Pigment Yellow 101 (Aldazingelb); C.I. Pigment Brown 22.
Anorganische Pigmente:Inorganic pigments:

  • Weißpigmente:    Titandioxid (C.I. Pigment White 6), Zinkweiß, Farbenzinkoxid, Bariumsulfat, Zinksulfid, Lithopone; Bleiweiß; Calziumcarbonat;White pigments: titanium dioxide (C.I. Pigment White 6), zinc white, color zinc oxide, barium sulfate, zinc sulfide, lithopone; White lead; calcium carbonate;
  • Schwarzpigmente:     Eisenoxidschwarz (C.I. Pigment Black 11), Eisen-ManganSchwarz, Spinellschwarz (C.I. Pigment Black 27); Ruß (C.I. Pigment Black 7);Black pigments: iron oxide black (C.I. Pigment Black 11), iron manganese black, spinel black (C.I. Pigment Black 27); Carbon black (C.I. Pigment Black 7);
  • Buntpigmente:    Chromoxid, Chromoxidhydratgrün; Chromgrün (C.I. Pigment Green 48); Cobaltgrün (C.I. Pigment Green 50); Ultramaringrün; Kobaltblau (C.I. Pigment Blue 28 und 36); Ultramarinblau; Eisenblau (C.I. Pigment Blue 27); Manganblau; Ultramarinviolett; Kobalt- und Manganviolett; Eisenoxidrot (C.I. Pigment Red 101); Cadmiumsulfoselenid (C.I. Pigment Red 108); Molybdatrot (C.I. Pigment Red 104); Ultramarinrot;
    Eisenoxidbraun, Mischbraun, Spinell- und Korundphasen (C.I. Pigment Brown 24, 29 und 31), Chromorange;
    Eisenoxidgelb (C.I. Pigment Yellow 42); Nickeltitangelb (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157 und 164); Chromtitangelb; Cadmiumsulfid und Cadmiumzinksulfid (C.I. Pigment Yellow 37 und 35); Chromgelb (C.I. Pigment Yellow 34), Zinkgelb, Erdalkalichromate; Neapelgelb; Bismutvanadat (C.I. Pigment Yellow 184);    Colored pigments: chromium oxide, chromium oxide hydrate green; Chrome green (CI Pigment Green 48); Cobalt green (CI Pigment Green 50); Ultramarine green; Cobalt blue (CI Pigment Blue 28 and 36); Ultramarine blue; Iron blue (CI Pigment Blue 27); Manganese blue; Ultramarine violet; Cobalt and manganese violet; Iron oxide red (CI Pigment Red 101); Cadmium sulphoselenide (CI Pigment Red 108); Molybdate red (CI Pigment Red 104); ultramarine;
    Iron oxide brown, mixed brown, spinel and corundum phases (CI Pigment Brown 24, 29 and 31), chrome orange;
    Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); Chromium titanium yellow; Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34), zinc yellow, alkaline earth dichromates; Naples yellow; Bismuth vanadate (CI Pigment Yellow 184);
  • Interferenzpigmente:    Metalleffektpigmente auf der Basis beschichteter Metallplättchen; Perlglanzpigmente auf der Basis metalloxidbeschichteter Glimmerplättchen; Flüssigkristallpigmente.Interference pigments: metallic effect pigments based on coated metal flakes; Pearlescent pigments based on metal oxide coated mica platelets; Liquid crystal pigments.

Als bevorzugte Pigmente (B) sind dabei Monoazopigmente (insbesondere verlackte BONS-Pigmente, Naphthol AS-Pigmente), Disazopigmente (insbesondere Diarylgelbpigmente, Bisacetessigsäureacetanilidpigmente, Disazopyrazolonpigmente), Chinacridonpigmente, Chinophthalonpigmente, Perinonpigmente, Phthalocyaninpigmente, Triarylcarboniumpigmente (Alkaliblaupigmente, verlackte Rhodamine, Farbstoffsalze mit komplexen Anionen), Isoindolinpigmente, Weißpigmente und Ruße zu nennen.Preferred pigments (B) are monoazo pigments (especially laked BONS pigments, Naphthol AS pigments), disazo pigments (especially diaryl, Bisacetessigsäureacetanilidpigmente, disazo pyrazolone pigments), quinacridone pigments, quinophthalone pigments, perinone pigments, phthalocyanine pigments, triarylcarbonium (alkali blue pigments, laked rhodamines, dye salts with complex Anions), isoindoline pigments, white pigments and carbon blacks.

Beispiele für besonders bevorzugte Pigmente sind im einzelnen: Ruß, Titandioxid, C.I. Pigment Yellow 138, C.I. Pigment Red 122 und 146, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3 und 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 und 43 und C.I. Pigment Green 7.Specific examples of particularly preferred pigments are: carbon black, titanium dioxide, C.I. Pigment Yellow 138, C.I. Pigment Red 122 and 146, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43 and C.I. Pigment Green 7.

Geeignete Stabilisatoren umfassen typische UV-Absorber wie Oxanilide, Triazine und Benzotriazol (letztere erhältlich als Tinuvin® -Marken der BASF) und Benzophenone. Diese können allein oder zusammen mit geeigneten Radikalfängern, beispielsweise sterisch gehinderten Aminen wie 2,2,6,6-Tetramethylpiperidin, 2,6-Di-tert.-butylpiperidin oder deren Derivaten, z. B. Bis-(2,2,6,6-tetra-methyl-4-piperidyl)sebacinat, oder Chinonmethide (wie Irgastab® UV 22) eingesetzt werden. Stabilisatoren werden üblicherweise in Mengen von 0,1 bis 0,5 Gew.-%, der Wirkstoffkomponente, bezogen auf die Zubereitung, eingesetzt.Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin® brands from BASF) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate, or quinone methides (such as Irgastab® UV 22) are used. Stabilizers are usually used in amounts of 0.1 to 0.5 wt .-%, the active ingredient component, based on the preparation.

Ein weiterer Aspekt der vorliegenden Erfindung ist ein Verfahren zum Bedrucken von flächigen oder dreidimensionalen, bevorzugt flächigen Substraten nach einem beliebigen Druckverfahren unter Verwendung von mindestens einer erfindungsgemäßen Druckfarbe. In einer bevorzugten Variante des erfindungsgemäßen Druckverfahrens druckt man mindestens eine erfindungsgemäße Druckfarbe auf ein Substrat und behandelt anschließend mit aktinischer Strahlung, beispielsweise UV-Strahlung und/oder Elektronenstrahlen, bevorzugt UV-Strahlung.Another aspect of the present invention is a method for printing flat or three-dimensional, preferably sheet-like substrates by any printing method using at least one printing ink according to the invention. In a preferred variant of the printing process according to the invention, at least one printing ink according to the invention is printed on a substrate and then treated with actinic radiation, for example UV radiation and / or electron beams, preferably UV radiation.

Druckverfahren, in denen die erfindungsgemäßen Druckfarben eingesetzt werden können sind bevorzugt Offsetdruck, Hochdruck, Flexodruck, Tiefdruck, Siebdruck und Tintenstrahldruck besonders bevorzugt sind Flexodruck und Offsetdruck.Printing processes in which the printing inks according to the invention can be used are preferably offset printing, high-pressure, flexographic printing, gravure printing, screen printing and ink-jet printing. Particular preference is given to flexographic printing and offset printing.

Bei den sogenannten mechanischen Druckverfahren wie Offsetdruck, Hochdruck, Flexodruck oder Tiefdruck wird die Druckfarbe durch Kontakt einer mit Druckfarbe versehenen Druckplatte oder Druckform mit dem Bedruckstoff auf den Bedruckstoff übertragen. UV härtbare Druckfarben für diese Anwendungen umfassen üblicherweise Reaktivverdünner , Bindemittel, Farbmittel, Initiatoren sowie ggf. verschiedene Additive. Bindemittel dienen zur Bildung des Farbfilms und der Verankerung der Bestandteile wie beispielsweise Pigmente oder Füllstoffe im Farbfilm. Je nach Konsistenz enthalten Druckfarben für diese Anwendungen üblicherweise zwischen 10 und 60 Gew. % Bindemittel. Reaktivverdünner dienen zur Einstellung der Verarbeitungsviskosität.In the so-called mechanical printing processes such as offset printing, high-pressure, flexographic printing or gravure printing, the printing ink is transferred to the printing material by contact of a printing plate provided with printing ink or printing form with the printing material. UV-curable printing inks for these applications usually include reactive diluents, binders, colorants, initiators and optionally various additives. Binders serve to form the color film and anchor the constituents such as pigments or fillers in the paint film. Depending on the consistency, printing inks for these applications usually contain between 10 and 60% by weight of binder. Reactive diluents are used to adjust the processing viscosity.

Drucklacke werden entweder als Grundierung auf den Bedruckstoff aufgetragen (sogenannte "primer") oder nach dem Druckvorgang als Überzug auf den bedruckten Bedruckstoff aufgetragen. Drucklacke werden beispielsweise zum Schutz des Druckbildes, zur Verbesserung der Haftung der Druckfarbe auf dem Bedruckstoff oder zu ästhetischen Zwecken eingesetzt. Die Auftragung erfolgt üblicherweise in-line oder offline mittels eines Lackierwerkes an der Druckmaschine.Printing varnishes are either applied to the substrate as a primer (so-called "primer") or applied to the printed substrate after the printing process as a coating. Printing lacquers are used, for example, to protect the printed image, to improve the adhesion of the printing ink to the printing substrate or for aesthetic purposes. The application is usually carried out in-line or offline by means of a coating unit on the printing press.

Drucklacke enthalten kein Farbmittel, sind aber abgesehen davon im Regelfalle ähnlich wie Druckfarben zusammengesetzt, und zeichnen sich durch die Abwesenheit des Farbmittels aus.Print varnishes do not contain a colorant but, apart from that, are generally similar in composition to printing inks and are distinguished by the absence of the colorant.

Druckfarben für mechanische Druckverfahren umfassen so genannte pastöse Druckfarben mit hoher Viskosität für den Offset-und Hochdruck sowie so genannte Flüssigdruckfarben mit vergleichsweise niedriger Viskosität für den Flexo- und Tiefdruck.Printing inks for mechanical printing include so-called pasty inks of high viscosity for offset and high pressure as well as so-called liquid inks of comparatively low viscosity for flexographic and gravure printing.

Die erfindungsgemäßen Tinten können beispielsweise eingesetzt werden als Ink-Jet-Flüssigkeit sowie für Flüssigtoner für elektrophotographische Druckverfahren.The inks according to the invention can be used, for example, as ink-jet liquid and for liquid toner for electrophotographic printing processes.

Gegebenenfalls kann, wenn mehrere Druckschichten der Druckfarben übereinander aufgetragen werden, nach jedem Druckvorgang eine Trocknung und/oder Strahlungshärtung erfolgen.Optionally, if a plurality of printing layers of the printing inks are applied one above the other, drying and / or radiation curing take place after each printing operation.

Die Strahlungshärtung erfolgt mit energiereichem Licht, z.B. UV-Licht oder Elektronenstrahlen. Die Strahlungshärtung kann auch bei höheren Temperaturen erfolgen.Radiation curing is performed with high energy light, e.g. UV light or electron beams. The radiation curing can also be carried out at higher temperatures.

Als Strahlungsquellen für die Strahlungshärtung geeignet sind z.B. Quecksilber-Niederdruckstrahler, -Mitteldruckstrahler mit Hochdruckstrahler sowie Leuchtstoffröhren, Impulsstrahler, Metallhalogenidstrahler, Elektronenblitzeinrichtungen, wodurch eine Strahlungshärtung ohne Photoinitiator möglich ist, oder Excimerstrahler sowie UV-LEDs. Die Strahlungshärtung erfolgt durch Einwirkung energiereicher Strahlung, also UV-Strahlung oder Tageslicht, vorzugsweise Licht im Wellenlängenbereich von λ=200 bis 700 nm strahlt, besonders bevorzugt von λ=200 bis 500 nm und ganz besonders bevorzugt λ=250 bis 420 nm, oder durch Bestrahlung mit energiereichen Elektronen (Elektronenstrahlung; 60 bis 300 keV). Als Strahlungsquellen dienen beispielsweise Hochdruckquecksilberdampflampen, Laser, gepulste Lampen (Blitzlicht), Halogenlampen, UV-LEDs oder Excimerstrahler. Die üblicherweise zur Vernetzung ausreichende Strahlungsdosis bei UV-Härtung liegt im Bereich von 30 bis 3000 mJ/cm2.Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, impulse lamps, metal halide, electronic flash devices, which radiation curing without photoinitiator is possible, or Excimerstrahler and UV LEDs. The radiation is cured by exposure to high-energy radiation, ie UV radiation or daylight, preferably light in the wavelength range of λ = 200 to 700 nm, particularly preferably from λ = 200 to 500 nm and most preferably λ = 250 to 420 nm, or by Irradiation with high-energy electrons (electron radiation, 60 to 300 keV). The radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps, UV LEDs or excimer radiators. The radiation dose for UV curing, which is usually sufficient for crosslinking, is in the range from 30 to 3000 mJ / cm 2 .

Selbstverständlich sind auch mehrere Strahlungsquellen für die Härtung einsetzbar, z.B. zwei bis vier.Of course, several radiation sources can be used for the curing, e.g. two to four.

Diese können auch in jeweils unterschiedlichen Wellenlängebereichen strahlen.These can also radiate in different wavelength ranges.

Die Bestrahlung kann gegebenenfalls auch unter Ausschluß von Sauerstoff, z. B. unter Inertgas-Atmosphäre, durchgeführt werden. Als Inertgase eignen sich vorzugsweise Stickstoff, Edelgase, Kohlendioxid, oder Verbrennungsgase.The irradiation may optionally also in the absence of oxygen, for. B. under inert gas atmosphere, are performed. As inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases.

Es stellt einen Vorteil der Polyurethane (A) und des erfindungsgemäßen Verfahrens dar, daß sich mit diesen Tinten, Druckfarben und Drucklacke herstellen lassen, deren Gehalt an extrahierbaren und/oder migrierbaren Bestandteilen verringert ist. Da der Photoinitiator in die erfindungsgemäßen Polyurethane eingebaut ist,. sind auch die Abbauprodukte der Photoinitiatoren zusätzlich in der Beschichtung fixiert, so daß sie in der Regel nicht oder wenig migrationsfähig sind. Dies hat zur Folge, daß mit den erfindungsgemäßen Polyurethanen wenig oder kein migrationsfähiger Anteil von Abbauprodukten von Photoinitiatoren, beispielsweise durch Extraktion der erhaltenen Beschichtungen, gefunden wird, wenn man diese mit Beschichtungen vergleicht, in denen der Zusatz von niedermolekularen, d.h. nicht einbaubaren Photoinitiatoren erforderlich ist. Durch den Verzicht auf Zinn als Katalysator in der Herstellung der Polyurethane (A) werden toxikologisch bedenkliche Metalle vermieden. Zudem ist die Viskosität der erfindungsgemäßen Formulierungen, Tinten, Drucklacken und Druckfarben in der Regel relativ gering, da die Polyurethane bevorzugt Allophanatgruppen aufweisen. Zusätzlich ist durch den Anteil an Wasser eine niedrigviskose Formulierung herstellbar, die die Einarbeitbarkeit der Polyurethane (A) in Tinten, Drucklacken und Druckfarben erleichtert.It is an advantage of the polyurethanes (A) and the process according to the invention that can be produced with these inks, printing inks and printing varnishes whose Content of extractable and / or migratable components is reduced. Since the photoinitiator is incorporated in the polyurethanes of the invention,. The decomposition products of the photoinitiators are additionally fixed in the coating, so that they are usually not or little migratory. This has the consequence that with the polyurethanes according to the invention little or no migrationsfähiger proportion of degradation products of photoinitiators, for example by extraction of the resulting coatings, is found, when compared with coatings in which the addition of low molecular weight, ie not incorporable photoinitiators is required , By eliminating tin as a catalyst in the production of polyurethanes (A) toxicologically hazardous metals are avoided. In addition, the viscosity of the formulations, inks, printing lacquers and printing inks according to the invention is generally relatively low, since the polyurethanes preferably have allophanate groups. In addition, a low-viscosity formulation can be produced by the proportion of water, which facilitates the incorporation of the polyurethanes (A) in inks, printing inks and printing inks.

In dieser Schrift verwendete ppm- und Prozentangaben beziehen sich, falls nicht anders angegeben, auf Gewichtsprozente und -ppm.Ppm and percentages used in this specification, unless otherwise indicated, are by weight percent and ppm.

Die folgenden Beispiele sollen die Erfindung erläutern, aber nicht auf diese Beispiele einschränken.The following examples are intended to illustrate but not to limit the invention.

BeispieleExamples

Bei Laromer® LR 8863 der BASF SE, Ludwigshafen, handelt es sich um ein handelsübliches Triacrylat von im statistischen Mittel 3,5-fach ethoxyliertem Trimethylolpropan.In Laromer ® LR 8863 from BASF SE, Ludwigshafen, Germany, is a commercially available triacrylate of 3.5 times ethoxylated trimethylolpropane statistical average.

Bei Laromer® 9000 der BASF SE, Ludwigshafen, handelt es sich um ein handelsübliches, allophanatgruppenhaltiges Polyisocyanat der obigen Formel (I), in dem Acrylatgruppen über Allophanatgruppen gebunden sind. Der NCO-Gehalt beträgt 14,5 bis 15,5 Gew%.Laromer® 9000 from BASF SE, Ludwigshafen, is a commercially available, allophanate-containing polyisocyanate of the above formula (I) in which acrylate groups are bonded via allophanate groups. The NCO content is 14.5 to 15.5% by weight.

Bei Irgacure® 2959 der BASF SE, Ludwigshafen, handelt es sich um einen handelsüblichen Photoinitiator vom α-Hydroxyketon-Typ (1-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-on).Irgacure ® 2959 from BASF SE, Ludwigshafen, Germany, is a commercially available photoinitiator from α-hydroxy ketone type (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane 1-one).

Bei Irgastab® UV22 der BASF SE, Ludwigshafen, handelt es sich um einen handelsüblichen Stabilisator aus Chinonmethid, gelöst in einem Acrylat von propoxyliertem Glycerin.In Irgastab UV22 ® from BASF SE, Ludwigshafen, Germany, is a commercially available stabilizer quinone dissolved in an acrylate of propoxylated glycerin.

Beispiel 1:Example 1:

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 120 Teile eines Isocyanatoacrylats (Laromer® LR9000), 79 Teile eines Photoinitiators (Irgacure® 2959), 0,1 Teile Borchi® Kat 24 (Wismut carboxylat) und 0,9 Teile eines weiteren Stabilisators (Irgastab® UV22) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C so lange reagieren bis der NCO Wert auf < 0,8% abgefallen war, gab die auf NCO berechnete equivalente Menge Ethanol zu, und ließ weiterreagieren bis der NCO Wert auf 0 abgefallen war. Dann ließ man abkühlen, gab 3% Wasser zu und füllte ab.86 parts of a polyether acrylate (Laromer ® LR 8863), 120 parts of a Isocyanatoacrylats (Laromer LR9000 ®), 79 parts of a photoinitiator (Irgacure ® 2959), 0.1 parts Borchi® Kat 24 (bismuth carboxylate) and 0.9 parts of another stabilizer (Irgastab UV22 ®) were charged to a reaction flask and heated to 80 ° C. The reaction was then allowed to proceed at 80-85 ° C until the NCO value had dropped to <0.8%, the ethanol added to NCO was added, and the reaction was allowed to continue until the NCO value dropped to zero. Then allowed to cool, added 3% water and filled.

Beispiel 1 a:Example 1 a:

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 100 Teile eines Isocyanatoacrylats (Laromer® LR9000), 79 Teile eines Photoinitiators (Irgacure® 2959), 0,1 Teile Borchi® Kat 24 (Wismut carboxylat) und 0,9 Teile eines weiteren Stabilisators (Irgastab® UV22) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C so lange reagieren bis der NCO Wert auf < 0,8% abgefallen war, gab die auf NCO berechnete equivalente Menge Ethanol zu, und ließ weiterreagieren bis der NCO Wert auf 0 abgefallen war. Dann ließ man abkühlen, gab 3% Wasser zu und füllte ab. Das GPC Spektrum zeigt, dass noch ca. 6% nicht umgesetztes Irgacure® 2959 vorhanden sind.86 parts of a polyether acrylate (Laromer ® LR 8863), 100 parts of a Isocyanatoacrylats (Laromer LR9000 ®), 79 parts of a photoinitiator (Irgacure ® 2959), 0.1 parts Borchi® Kat 24 (bismuth carboxylate) and 0.9 parts of another stabilizer (Irgastab UV22 ®) were charged to a reaction flask and heated to 80 ° C. The reaction was then allowed to proceed at 80-85 ° C until the NCO value had dropped to <0.8%, the ethanol added to NCO was added, and the reaction was allowed to continue until the NCO value dropped to zero. Then allowed to cool, added 3% water and filled. The GPC spectrum shows that about 6% unreacted Irgacure® 2959 is still present.

Vergleichsbeispiel 1:Comparative Example 1

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 120 Teile eines Isocyanatoacrylats (Laromer® LR9000), und 79 Teile eines Photoinitiators (Irgacure® 2959) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C weiterreagieren, um den NCO Wert auf < 0,8% zu bringen. Nach ca. 20 Stunden war der Photoinitiator noch nicht vollständig umgesetzt. Bevor der Wert jedoch < 0,8% erreichte (ca. 12 h), trat Vernetzung ein.86 parts of a polyether acrylate (Laromer LR 8863), 120 parts of a Isocyanatoacrylats (Laromer LR9000 ®) and 79 parts of a photoinitiator (Irgacure ® 2959) were charged to a reaction flask and heated to 80 ° C. Then allowed to react at 80-85 ° C to bring the NCO value to <0.8%. After about 20 hours, the photoinitiator was not fully reacted. However, before the value reached <0.8% (about 12 hours), crosslinking occurred.

Vergleichsbeispiel 1 zeigt, daß es erforderlich ist mit einer Komponente (f) die freien NCO-Gruppen umzusetzen.Comparative Example 1 shows that it is necessary to react with a component (f) the free NCO groups.

Vergleichsbeispiel 2:Comparative Example 2:

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 120 Teile eines Isocyanatoacrylats (Laromer® LR9000), 79 Teile eines Photoinitiators (Irgacure® 2959) und 0,9 Teile eines weiteren Stabilisators (Irgastab® UV22) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C so lange reagieren bis der NCO Wert auf < 0,8% abgefallen war, gab die auf NCO berechnete equivalente Menge Ethanol zu, und ließ weiterreagieren bis der NCO Wert auf 0 abgefallen war. Dann ließ man abkühlen und gab 5% Wasser zu. Das Reaktionsgemisch wurde trüb.86 parts of a polyether acrylate (Laromer ® LR 8863), 120 parts of a Isocyanatoacrylats (Laromer ® LR9000), 79 parts of a photoinitiator (Irgacure ® 2959) and 0.9 parts of another stabilizer (Irgastab ® UV22) were charged to a reaction flask and Heated to 80 ° C. The mixture was then allowed to react at 80-85 ° C until the NCO value had dropped to <0.8%, gave the equivalent amount calculated on NCO Ethanol, and allowed to react until the NCO value had dropped to 0. Then allowed to cool and gave 5% water. The reaction mixture became cloudy.

Vergleichsbeispiel 2 zeigt, daß die erfindungsgemäßen Formulierungen bei Zugabe von zuviel Wasser eintrüben.Comparative Example 2 shows that the formulations according to the invention cloud on addition of too much water.

Beispiel 2:Example 2:

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 120 Teile eines Isocyanatoacrylats (Laromer® LR9000), 79 Teile eines Photoinitiators (Irgacure® 2959) 50 ppm Borchi® Kat 24 (Bismut carboxylat) und 0,015 Teile eines weiteren Stabilisators (Irgastab® UV22) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C so lange reagieren bis der NCO Wert auf < 0,8% abgefallen war, gab die auf NCO berechnete equivalente Menge Ethanol zu, und ließ weiterreagieren bis der NCO Wert auf 0 abgefallen war. Das GPC Chromatogramm zeigte eine vollständige Umsetzung des Photoinitiators. Dann gab man ein weiteres Teil des Stabilisators UV22 zu, ließ abkühlen, gab 2% Wasser zu und füllte ab.86 parts of a polyether acrylate (Laromer ® LR 8863), 120 parts of a Isocyanatoacrylats (Laromer ® LR9000), 79 parts of a photoinitiator (Irgacure ® 2959) 50 ppm Borchi® Kat 24 (bismuth carboxylate) and 0.015 parts of another stabilizer (Irgastab ® UV22 ) were placed in a reaction flask and heated to 80 ° C. The reaction was then allowed to proceed at 80-85 ° C until the NCO value had dropped to <0.8%, the ethanol added to NCO was added, and the reaction was allowed to continue until the NCO value dropped to zero. The GPC chromatogram showed complete conversion of the photoinitiator. Then another portion of the stabilizer UV22 was added, allowed to cool, 2% water added and bottled.

Beispiel 3:Example 3:

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 120 Teile eines Isocyanatoacrylats (Laromer® LR9000), 79 Teile eines Photoinitiators (Irgacure® 2959) 50 ppm Borchi® Kat22 (Zink carboxylat) und 0,015 Teile eines weiteren Stabilisators (Irgastab® UV22) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C so lange reagieren bis der NCO Wert auf < 0,8% abgefallen war, gab die auf NCO berechnete equivalente Menge Ethanol zu, und ließ weiterreagieren bis der NCO Wert auf 0 abgefallen war. Das GPC Chromatogramm zeigte eine vollständige Umsetzung des Photoinitiators. Dann gab man 1,5 weitere Teile des Stabilisators UV22 zu, ließ abkühlen, gab 2% Wasser zu und füllte ab.86 parts of a polyether acrylate (Laromer ® LR 8863), 120 parts of a Isocyanatoacrylats (Laromer ® LR9000), 79 parts of a photoinitiator (Irgacure ® 2959) 50 ppm Borchi® Kat22 (zinc carboxylate) and 0.015 parts of another stabilizer (Irgastab ® UV22) were placed in a reaction flask and heated to 80 ° C. The reaction was then allowed to proceed at 80-85 ° C until the NCO value had dropped to <0.8%, the ethanol added to NCO was added, and the reaction was allowed to continue until the NCO value dropped to zero. The GPC chromatogram showed complete conversion of the photoinitiator. Then, 1.5 more parts of the stabilizer UV22 were added, allowed to cool, 2% water was added to and filled.

Beispiel 4:Example 4:

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 120 Teile eines Isocyanatoacrylats (Laromer® LR9000), 79 Teile eines Photoinitiators (Irgacure® 2959), 50 ppm Tetrabutyl ortho Titanat und 0,015 Teile eines weiteren Stabilisators (Irgastab® UV22) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C so lange reagieren bis der NCO Wert auf < 0,8% abgefallen war, gab die auf NCO berechnete equivalente Menge Ethanol zu, und ließ weiterreagieren bis der NCO Wert auf 0 abgefallen war. Das GPC Chromatogramm zeigte eine vollständige Umsetzung des Photoinitiators. Dann gab man 1,5 weitere Teile des Stabilisators UV22 zu, ließ abkühlen, gab 2% Wasser zu und füllte ab.86 parts of a polyether acrylate (Laromer ® LR 8863), 120 parts of a Isocyanatoacrylats (Laromer ® LR9000), 79 parts of a photoinitiator (Irgacure ® 2959), 50 ppm Tetrabutyl ortho titanate and 0.015 parts of another stabilizer (Irgastab ® UV22) were mixed in a Submitted reaction flask and heated to 80 ° C. The reaction was then allowed to proceed at 80-85 ° C until the NCO value had dropped to <0.8%, the ethanol added to NCO was added, and the reaction was allowed to continue until the NCO value dropped to zero. The GPC chromatogram showed complete conversion of the photoinitiator. Then, 1.5 more parts of the stabilizer UV22 were added, allowed to cool, 2% water was added to and filled.

Beispiel 5:Example 5:

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 120 Teile eines Isocyanatoacrylats (Laromer® LR9000), 79 Teile eines Photoinitiators (Irgacure® 2959) 50 ppm Borchi® Kat 315 Bismut carboxylat) und 0,015 Teile eines weiteren Stabilisators (Irgastab® UV22) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C so lange reagieren bis der NCO Wert auf < 0,8% abgefallen war, gab die auf NCO berechnete equivalente Menge Ethanol zu, und ließ weiterreagieren bis der NCO Wert auf 0 abgefallen war. Das GPC Chromatogramm zeigte eine vollständige Umsetzung des Photoinitiators. Dann gab man 1,5 weitere Teile des Stabilisators UV22 zu, ließ abkühlen, gab 2% Wasser zu und füllte ab.86 parts of a polyether acrylate (Laromer ® LR 8863), 120 parts of a Isocyanatoacrylats (Laromer ® LR9000), 79 parts of a photoinitiator (Irgacure ® 2959) 50 ppm Borchi® Kat carboxylate 315 bismuth) and 0.015 parts of another stabilizer (Irgastab ® UV22) were placed in a reaction flask and heated to 80 ° C. The reaction was then allowed to proceed at 80-85 ° C until the NCO value had dropped to <0.8%, the ethanol added to NCO was added, and the reaction was allowed to continue until the NCO value dropped to zero. The GPC chromatogram showed complete conversion of the photoinitiator. Then, 1.5 more parts of the stabilizer UV22 were added, allowed to cool, 2% water was added to and filled.

Beispiel 6:Example 6:

86 Teile eines Polyetheracrylates (Laromer® LR 8863), 120 Teile eines Isocyanatoacrylats (Laromer® LR9000), 79 Teile eines Photoinitiators (Irgacure® 2959) 50 ppm Borchi® Kat 315 Bismuth carboxylat) und 0,015 Teile eines weiteren Stabilisators (Irgastab® UV22) wurden in einem Reaktionskolben vorgelegt und auf 80°C erhitzt. Dann ließ man bei 80-85°C so lange reagieren bis der NCO Wert auf < 0,8% abgefallen war, gab die auf NCO berechnete equivalente Menge Lutensol TO3 (C13 alkohol ethoxylat, BASF SE) zu, und ließ weiterreagieren bis der NCO Wert auf 0 abgefallen war. Das GPC Chromatogramm zeigte eine vollständige Umsetzung des Photoinitiators. Dann gab man 1,5 weitere Teile des Stabilisators UV22 zu, ließ abkühlen, gab 2% Wasser zu und füllte ab.86 parts of a polyether acrylate (Laromer ® LR 8863), 120 parts of a Isocyanatoacrylats (Laromer ® LR9000), 79 parts of a photoinitiator (Irgacure ® 2959) 50 ppm Borchi® Kat 315 Bismuth carboxylate) and 0.015 parts of another stabilizer (Irgastab ® UV22) were placed in a reaction flask and heated to 80 ° C. Then allowed to react at 80-85 ° C until the NCO value had fallen to <0.8%, the calculated NCO equivalent amount of Lutensol TO3 (C13 alcohol ethoxylate, BASF SE) to, and allowed to react until the NCO Value had dropped to 0. The GPC chromatogram showed complete conversion of the photoinitiator. Then, 1.5 more parts of the stabilizer UV22 were added, allowed to cool, 2% water was added to and filled.

Anwendungsbeispieleapplications Beispiel 7Example 7

Ein Produkt wurde analog Beispiel 1 als 70 Gew%-ige Lösung in Laromer® LR 8863 ohne Zugabe von Wasser hergestellt und mit verschiedenen Mengen Wasser vermischt und das Aussehen sowie die Viskosität geprüft. Viskosität bei 25 °C Fließfähigkeit bei 25°C Mischbarkeit Ohne 600 Pas Nein Klar 1 % Wasser 322 Pas Schlecht Klar 2% Wasser 170 Pas Gut Klar 5% Wasser 82 Pas Sehr gut Trüb A product was prepared analogously to Example 1 as a 70 wt% solution in Laromer ® LR 8863 without the addition of water and mixed with various amounts of water and the appearance and the viscosity tested. Viscosity at 25 ° C Fluidity at 25 ° C Miscibility Without 600 pas No Clear 1% water 322 pas Bad Clear 2% water 170 pas Well Clear 5% water 82 pas Very well cloudy

Man sieht, daß die Formulierung ohne Zugabe von Wasser nicht fließfähig ist und bei Zugabe von zuviel Wasser eintrübt. Mithin bleibt ein enges Fenster, in dem sowohl die Viskosität als auch die Anwendungseigenschaften günstig sind.It can be seen that the formulation is not flowable without addition of water and clouding on addition of too much water. Consequently, a narrow window remains, in which both the viscosity and the application properties are favorable.

Beispiel 8Example 8

Verschiedene einbaubare Photoinitiatoren gemäß der vorliegenden Erfindung und gemäß der DE 10 2006 047863 wurden hergestellt und mit strahlungshärtbaren Acrylaten zu einem Drucklack formuliert.Various incorporable photoinitiators according to the present invention and according to the DE 10 2006 047863 were prepared and formulated with radiation-curable acrylates to a pressure varnish.

Beispiel 5 aus DE 10 2006 047863 wurde dabei wiederholt und bezogen auf dessen Photoinitiatorgehalt als reiner Initiator betrachtet (Vergleich a) bzw. bezogen auf dessen Gehalt an Reaktivverdünner als Beschichtungsmasse (Vergleich c).Example 5 from DE 10 2006 047863 Was repeated and considered based on the photoinitiator content as a pure initiator (Comparison a) or based on its content of reactive diluents as a coating composition (Comparison c).

Mit den Formulierungen wurden die Härtungsgeschwindigkeit, die Viskosität, der Glanz und die Abriebstabilität, sowie die Lösemittelbeständigkeit bestimmt.
Der Lack wurde dazu mit einem 6µm Spiralrakel auf Leneta Karton beschichtet und mit einer UV-Anlage M-30-2x1-BLKU der Fa. IST die mit einer, in der Leistung, regelbaren 200W/cm Hg-Mitteldrucklampe ausgerüstet ist, belichtet. Die Härtungsgeschwindigkeit wurde mit dem Fingernagel bestimmt. Wenn die Oberfläche keine Kratzer aufwies, galt der Lack als gehärtet.The formulations were used to determine the rate of cure, the viscosity, the gloss and the abrasion stability, and also the solvent resistance.
The varnish was coated with a 6μm spiral blade on Leneta cardboard and exposed with a UV-system M-30-2x1-BLKU of the company IST, which is equipped with an adjustable 200W / cm Hg medium pressure lamp. The rate of cure was determined with the fingernail. If the surface had no scratches, the paint was considered hardened.

Der Glanz wurde mit einem Byk-Gardner Micro-Tri-Gloss Glanzmessgerät bei 60° auf Leneta Karton bestimmt. Nach je 5 Doppelhüben mit einem Scotch Brite® Pad Typ 07448 (Fa. 3M) wurde die Abriebfestigkeit mittels des Glanzabfalls bestimmt Vergleich a Vergleich b Erfindungsgemäß Vergleich c Beispiel 5 aus DE 10 2006 047863 15,0 Beispiel 2 aus DE 10 2006 047863 (d.h. ohne Wasser) 15 Beispiel 5 d.h. enthaltend 2 Gew% Wasser 15,0 Beispiel 5 aus DE 10 2006 047863 100 Laromer® LR 8986 27 27 27 Laromer® PO77F 33 33 33 Tripropylenglykol diacrylat 39,8 39,8 39,8 EFKA 7305 0,2 0,2 0,2 Summe 100 100 100 Härtungsgeschwindigkeit 3m/min 18m/min 15m/min 5m/min Viskosität des Reaktionsgemischs 0,2Pas 600Pas 170Pas - Viskosität der Beschichtungsmasse 0,3 Pas 0,6Pas 0,4Pas 0,2Pas Glanz 85 92 92 70 Abriebsfestigkeit (Restglanz nach 5 Doppelhüben mit Scotch Brite 07448 (Fa. 3M)) 49 77 77 61 MEK Festigkeit Doppelhübe <10 30 30 30 Bei Laromer® LR 8986 handelt es sich um ein handelsübliches Gemisch aus Epoxyacrylat und Triacrylat von ethoxyliertem Trimethylolpropan der BASF SE, Ludwigshafen.
Bei Laromer® PO 77F handelt es sich um ein handelsübliches aminmodifiziertes etwa trifunktionelles Polyetheracrylat der BASF SE, Ludwigshafen.
Bei EFKA 7305 handelt es sich um ein handelsübliches Additiv für Verlauf und Oberflächenglätte der BASF SE, Ludwigshafen. The gloss was determined with a Byk-Gardner Micro-Tri-Gloss Glossmeter at 60 ° on Leneta cardboard. After 5 double strokes each with a Scotch Brite® pad type 07448 (3M), the abrasion resistance was determined by means of the gloss drop Comparison a Comparison b According to the invention Comparison c Example 5 from DE 10 2006 047863 15.0 Example 2 from DE 10 2006 047863 (ie without water) 15 Example 5 ie containing 2% by weight of water 15.0 Example 5 from DE 10 2006 047863 100 Laromer® LR 8986 27 27 27 Laromer® PO77F 33 33 33 Tripropylene glycol diacrylate 39.8 39.8 39.8 EFKA 7305 0.2 0.2 0.2 total 100 100 100 cure rate 3m / min 18m / min 15m / min 5m / min Viscosity of the reaction mixture 0,2Pas 600Pas 170Pas - Viscosity of the coating composition 0.3 Pas 0,6Pas 0,4Pas 0,2Pas shine 85 92 92 70 Abrasion resistance (residual gloss after 5 double strokes with Scotch Brite 07448 (3M company)) 49 77 77 61 MEK strength double strokes <10 30 30 30 Laromer® LR 8986 is a commercial mixture of epoxy acrylate and triacrylate of ethoxylated trimethylolpropane from BASF SE, Ludwigshafen.
Laromer® PO 77F is a commercially available amine-modified, approximately trifunctional polyether acrylate from BASF SE, Ludwigshafen.
EFKA 7305 is a commercial additive for smoothness and surface smoothness of BASF SE, Ludwigshafen.

Man sieht, daß im erfindungsgemäßen Beispiel durch Zugabe von Wasser eine Absenkung der Viskosität auch des Drucklackes möglich ist. Jedoch ist im Vergleich b das Reaktionsgemisch gemäß Beispiel 2 aus DE 10 2006 047863 (d.h. ohne Wasser) nicht fließfähig und somit schlecht formulierbar, außerdem ist die Viskosität des Drucklacks für ein optimales Beschichtungergebnis zu hoch.It can be seen that in the example according to the invention by adding water a lowering of the viscosity of the printing lacquer is possible. However, in comparison b, the reaction mixture according to Example 2 is made DE 10 2006 047863 (ie without water) not flowable and thus poorly formulated, also the viscosity of the printing ink for an optimal coating result is too high.

Aus den Vergleichen a und c zeigt sich, daß Beispiel 5 aus DE 10 2006 047863 im direkten Vergleich mit dem erfindungsgemäßen Beispiel schlechtere anwendungstechnische Eigenschaften, wie einen geringeren Restglanz und schlechtere Abriebfestigkeit aufweist und eine ungenügende Reaktivität zeigt.From the comparisons a and c, it turns out that example 5 is DE 10 2006 047863 in direct comparison with the example according to the invention has poorer application properties, such as a lower residual gloss and lower abrasion resistance and shows insufficient reactivity.

Beispiel 9Example 9

Die erfindungsgemäßen Photoinitiatoren aus Beispiel 5 (in Beispiel 9a) und Beispiel 6 (in Beispiel 9b) wurden in einer Offsetdruckfarbe eingesetzt, als Vergleich wurde Irgacure® 2959 gewählt. Die Konzentration an Irgacure® 2959 im Vergleichsbeispiel entsprach dabei der Konzentration des Chromophors in dem erfindungsgemäßen Photioinitiator. Dazu wurden alle Komponenten vermischt und auf einer Labordrehwalze der Fa. Bühler dispergiert, bis alle Photoinitiatoren gelöst waren.
Dann wurde die Druckfarbe mit einem Offsetprobedruckgerät der Fa. Prüfbau auf gestrichenen Karton mit einem Auftragsgewicht von 1,7g/m2 gedruckt und mit einer UV Belichtungseinheit M-30-2x1-BLKU der Fa. IST bei 80W/cm (Aluminiumreflektoren) belichtet. Die Durchhärtung wurde mit dem REL Tester (PTC-Prüfgerät, Fa. Prüfbau) bestimmt. Die Farbdichte wurde mit einem Densitometer SPM55 der Fa. Gretag-Macbeth bestimmt. Bsp. 9a Bsp. 9b Vergleich Heliogen Blau D7088 16 16 16 Ebecryl 657 19 19 20 Ebecryl 3700 17 17 18 Laromer® PE 9084 19 19 20 Laromer® GPTA 16 16 19 Luwax® AF30 1 1 1 Irgacure® 369 4 4 4 Irgacure® 2959 2 Initiator aus Beispiel 5 8 Initiator aus Beispiel 6 8 Summe 100 100 100 Härtungsgeschwindigkeit m/min 180 180 130 Farbdichte des Andrucks 1,41 1,53 1,37 The photoinitiators according to the invention from Example 5 (in Example 9a) and Example 6 (in Example 9b) were used in an offset printing ink; for comparison, Irgacure® 2959 was chosen. The concentration of Irgacure® 2959 in the comparative example corresponded to the concentration of the chromophore in the photoinitiator according to the invention. For this purpose, all components were mixed and dispersed on a laboratory lathe Fa. Buhler until all photoinitiators were dissolved.
The printing ink was then printed on a coated cardboard with an application weight of 1.7 g / m 2 using an offset proofing device from the firm of Prüfbau and exposed to an UV exposure unit M-30-2x1-BLKU from the company IST at 80 W / cm (aluminum reflectors). The hardening was determined with the REL tester (PTC test device, Fa. Prüfbau). The color density was determined using a densitometer SPM55 from Gretag-Macbeth. Ex. 9a Example 9b comparison Heliogen Blue D7088 16 16 16 Ebecryl 657 19 19 20 Ebecryl 3700 17 17 18 Laromer® PE 9084 19 19 20 Laromer® GPTA 16 16 19 Luwax® AF30 1 1 1 Irgacure® 369 4 4 4 Irgacure® 2959 2 Initiator from example 5 8th Initiator from Example 6 8th total 100 100 100 Curing speed m / min 180 180 130 Color density of the proof 1.41 1.53 1.37

Überraschend zeigt sich, dass die erfindungsgemäßen Initiatoren bei gleicher Chromphorkonzentration sogar eine deutlich höhere Härtungsgeschwindigkeit als das Vergleichsbeispiel aufweisen. Die Farbdichte als Maß für die Intensität des Farbeindrucks ist bei Beispiel 9b, bei dem ein Fettsäurealkohol eingesetzt wurde, sogar höher als bei den anderen Versuchen, was auch auf eine dispergierende Wirkung des erfindungsgemäßen Photoinitiators hinweist.Surprisingly, it is found that the initiators according to the invention even have a significantly higher curing rate than the comparative example at the same chromophore concentration. The color density as a measure of the intensity of the color impression is even higher in Example 9b, in which a fatty acid alcohol was used, than in the other experiments, which also indicates a dispersing effect of the photoinitiator according to the invention.

Claims (12)

  1. A process for preparing incorporable photoinitiators of low viscosity, comprising the steps of
    1) synthesizing a polyurethane A comprising as synthesis components
    (a) at least one organic polyisocyanate containing allophanate groups and having an NCO functionality of at least 2, synthesized from aliphatic C4 to C20 alkylene diisocyanates,
    (b) at least one compound having in each case at least one isocyanate-reactive group and at least one radically polymerizable unsaturated group,
    (c) at least one photoinitiator having at least one isocyanate-reactive group,
    (d) optionally at least one further diisocyanate and/or polyisocyanate, which is different from the compound (a),
    (e) optionally at least one compound having at least two isocyanate-reactive groups, and also
    (f) optionally at least one compound having precisely one isocyanate-reactive group
    under anhydrous conditions, wherein the polyurethanes (A) are prepared in the presence of less than 1000 ppm by weight of a bismuth-, zinc- and/or titanium-containing compound and in a step 2) the polyurethane (A) obtained from step 1) is mixed with 0.5% to 4% by weight of water, based on the amount of polyurethane (A).
  2. The process according to claim 1, wherein component (b) is bonded via allophanate groups to component (a).
  3. The process according to claim 2, wherein the amount of allophanate groups (calculated as C2N2HO3 = 101 g/mol) is 1% to 28% by weight.
  4. The process according to any of the preceding claims, wherein the compounds (c) are
    Figure imgb0009
    Figure imgb0010
     in which
    R3, R4, and R5 each independently of one another are hydrogen, an alkyl group containing 1 to 4 carbon atoms or an alkyloxy group containing 1 to 4 carbon atoms,
    p may be 0 (zero) or an integer from 1 to 10, and
    Yi for i = 1 to p independently of one another may be selected from the group of CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O-, and CHPh-CH2-O-, preferably from the group of -CH2-CH2-O-, -CH2-CH(CH3)-O-, and CH(CH3)-CH2-O-, and more preferably -CH2-CH2-O-.
  5. The process according to any of the preceding claims, wherein the compound (c) is selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-hydroxy-1-[4-[hydroxy[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methyl-propan-1-one, [4-[3-(4-benzoylphenoxy)-2-hydroxypropoxy]phenyl]phenylmethanone, benzoin, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, 7H-benzoin methyl ether, 2-hydroxy-2,2-dimethylacetophenone, and 1-hydroxy-acetophenone.
  6. The process according to any of the preceding claims, wherein the compound (f) comprises alkoxylated aliphatic alcohols of the formula

            R9-O-[-Zi-]q-H

    in which
    R9 is an alkyl radical having 1 to 20 carbon atoms, preferably 10 to 20 carbon atoms,
    q is a positive integer from 1 to 15, preferably 1 to 10, and
    Zi for i = 1 to q independently of one another may be selected from the group of CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-,
    -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-0-, and CHPh-CH2-O-, preferably from the group of -CH2-CH2-O-, -CH2-CH(CH3)-O-, and CH(CH3)-CH2-O-, and more preferably -CH2-CH2-O-.
  7. The process according to any of the preceding claims, wherein the bismuth-, zinc- and/or titanium-containing compound is selected from the group consisting of zinc carboxylates of carboxylates which have at least six carbon atoms, bismuth carboxylates of carboxylates which have at least six carbon atoms, and titanium tetraalcoholates Ti(OR)4 of alcohols ROH having 1 to 8 carbon atoms.
  8. A formulation of incorporable photoinitiators, consisting of at least one polyurethane A as defined in claim 1, and also 0.5% to 4% by weight of water, based on the amount of polyurethane (A), and also
    optionally at least one polyfunctional polymerization compound (B).
  9. An ink, printing-ink or print varnish comprising at least one polyurethane A as defined in claim 1,
    and also, in addition to the polyurethane (A),
    0.5 to 4% by weight of water, based on the amount of polyurethane (A),
    optionally at least one pigment,
    at least one polyfunctional polymerizable compound (B),
    optionally at least one further photoinitiator, and also
    optionally additives typical of printing-inks.
  10. The ink, printing-ink or print varnish according to claim 9, wherein the optional at least one further photoinitiator is selected from the group consisting of 2,4,6-trimethylbenzoyldiphenyl¬phosphine oxide, ethyl 2,4,6-trimethylbenzoyl¬phenyl-phosphinate, bis(2,4,6-tri¬methylbenzoyl)phenylphosphine oxide, 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-(p-tolylmethyl)butan-1-one, 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one, polymeric benzophenone derivatives, polymeric thioxanthone derivatives, polymeric α-amino ketones, and silsesquioxane compounds having at least one initiating group.
  11. The use of a printing-ink according to claim 10 for printing polyamides, polyethylene, polypropylene, polyesters, polyethylene terephthalate, polystyrene, paper, paperboard, cardboard, plastics-coated paper, plastics-coated paperboard or plastics-coated cardboard, aluminum or aluminum-coated polymeric films.
  12. The use of substrates selected from the group consisting of polyamide, polyethylene, polypropylene, polyesters, polyethylene terephthalate, polystyrene, paper, paperboard, cardboard, plastics-coated paper, plastics-coated paperboard or plastics-coated cardboard, aluminum or aluminum-coated polymeric films, printed with a printing-ink according to claim 10, as packaging materials for foods, cosmetics, and pharmaceuticals.
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